JP6600361B2 - Cold water laundry detergent - Google Patents

Description

  The present invention relates to laundry detergents useful for cold water cleaning. The detergent comprises a lipase and a medium chain head group surfactant or an alkylene crosslinking surfactant.

  Surfactants are an essential component of household and commercial detergents, agricultural products, personal care products, laundry detergents, oilfield chemicals, special foams, and many other daily necessities.

  Modern laundry detergents work well for removing a variety of soils from fabrics when warm or hot water is used in the wash cycle. Even the oil stains are softened or dissolved by the warm temperature. This helps to assist the surfactant in removing dirt from the fabric. However, hot water or hot water is not always desirable in cleaning. Hot or hot water tends to fade in color and may accelerate fabric degradation. Furthermore, due to the energy cost of heating the water for washing, cold water cleaning becomes more economically desirable and can be used without destroying the environment. In many parts of the world, only cold water can be used for laundry items.

  Needless to say, laundry detergents have been developed today that are designed to work well in hot, hot or cold water. One common cold water detergent comprises, among other conventional components, one nonionic surfactant (aliphatic alcohol ethoxylate) and two anionic surfactants (linear alkylbenzene sulfonate and fatty acid). Group alcohol ethoxylate sulfonate). Commercial cold water detergents tend to work well against a wide variety of common stains, but with such commercial cold water detergents, fat stains, especially bacon fat, beef tallow, butter, cooked heads, and this It is difficult to remove something similar to These stains are often deposited as liquids, but immediately solidify and become firmly attached to the fabric fibers. In particular, in a cold water washing cycle, the surfactant often does not surpass the problem of wetting these liquefied fat stains and liquefying them.

Most surfactants used in laundry detergents have a polar head and a non-polar tail. Polar groups (sulfates, sulfonates, amine oxides, etc.) are usually located at one end of the chain. In order to improve the solubility of the surfactant in cold water, in particular, a branched part may be introduced into a surfactant having a long chain length (C _{14 to} C ₃₀ ). There is little evidence to improve. Furthermore, branched surfactants may even protect polar groups at or near the chain end (see, for example, Patent Literatures 1 to 4).

  Secondary alkyl sulfate (SAS) surfactants are known and are used in laundry detergents. In general, these materials have sulfate groups randomly distributed along the hydrocarbyl skeleton. In some cases, the random structure results from the addition of sulfuric acid across the carbon-carbon double bonds in the internal olefin mixture and is accompanied by isomerization of the double bonds under strong acidity. A commercially available SAS from Clariant under the trademark Hostaspur® is made using a Hoechst light / water process. In the process, n-paraffins are reacted with sulfur dioxide and oxygen in the presence of water and ultraviolet light, followed by neutralization to produce secondary alkyl monosulfates as the main products.

Secondary alkyl sulfates in which a sulfate group is present at the 2-position or 3-position of the alkyl chain are produced (see, for example, Patent Documents 5 to 8). These are used to produce agglomerated high density detergent compositions comprising linear alkyl benzene sulfates, aliphatic alcohol sulfates, and aliphatic alcohol ether sulfates. Similarly, Patent Document 9 discloses a secondary laundry detergent-containing powder laundry detergent. In the laundry detergent, the alkyl chain is preferably C _{12 to} C ₁₈ and the sulfate group is preferably located at the 2-position.

Longer chain surfactants (C ₁₄ -C ₃₀ ) have been produced in which the polar group is located at the central carbon of the chain, but such compositions have not been evaluated for use in cold water laundry detergents. For example, U.S. Patent No. 6,057,031 teaches secondary alcohol alkoxylates capped with alkylene oxides as surfactants. In some examples, the —OH group, originally derived from alcohol, is located on the central carbon of the alkyl chain, in particular 8-hexadecanol and 6-tetradecanol. As another example, sodium 9-octadecyl sulfonate has been synthesized and taught as a surfactant for use in enhanced oil recovery processes (see Non-Patent Document 1 and Non-Patent Document 2). Sodium 8-hexadecyl sulfonate has been reported for use in powder dishwashing detergents (see, for example, US Pat.

  Numerous researchers have studied a series of secondary alcohol sulfates in which the sulfate groups move systematically along the alkyl chain because sulfate groups have different surfactant properties. This is to understand the effect on the environment. For example, Evans is a series of secondary alcohol sulfates containing sodium sulfate of 7-tridecanol, 8-pentadecanol, 8-hexadecanol, 9-septadecanol, 10-nonadecanol, and 15-nonacosanol (C29). Salts were prepared and the critical micelle concentration and other properties were measured (Non-patent Document 3). More recently, Xue-Gong Lei et al. Evaluated long-chain alcohol sulfate (C21 +) with a medium-chain branch as part of membrane modeling studies (Non-Patent Document 4).

  Dreger et al. Prepared a secondary alcohol sulfate having 11 to 19 carbons (Non-patent Document 5). Some of these are “symmetric secondary alcohol sulfates” (eg, sodium 7-tridecyl sulfate or sodium 8-pentadecyl sulfate). In the sulfate, the sulfate group was bonded to the central carbon. The detergency of these compositions was evaluated in warm water (43 ° C.). The author concluded that “when other factors are the same, the closer the polar group is to the end of the linear alcohol sulfate, the better the detergency”. The performance in cold water was not evaluated.

  Similarly, Finger et al. Studied the effect of alcohol structure and molecular weight on the properties of the corresponding sulfate and ethoxylate sulfates (Non-Patent Document 6). The author included sodium 7-tridecyl sulfate and sodium 7-pentadecyl sulfate in the study. The authors concluded that moving the polar group away from the terminal position generally reduces the cleaning power and foaming performance in cotton.

Surfactants in which polar groups are separated from the main alkyl chain by alkylene bridges are known. Some methylene cross-linking surfactants of this type are derived from “Guerbet” alcohol. Gervet alcohol can be made by dimerizing linear or branched aliphatic alcohols using basic catalysts with chemistry first discovered in the 19th century. The alcohol has a —CH ₂ — bridge to a hydroxyl group near the center of the alkyl chain and can be converted to alkoxylates, sulfates, and ether sulfates (see, eg, Non-Patent Document 7). ). It is not explicitly shown that garvet derivatives have any particular advantages for cold water cleaning.

Surprisingly, few references disclose surfactants that exhibit improved cleaning when using cold water (ie, below 30 ° C.). U.S. Patent No. 6,057,032 teaches a dimerized alcohol composition and a biodegradable surfactant made from the alcohol composition and having cold water cleaning performance. In some instances, it is provided that it exhibits improved cold water cleaning performance in oil (multiple sebum) soils when compared to sulfated Neodol® C ₁₄ -C ₁₅ alcohol. After being made by dimerizing internal or alpha olefins (preferably internal olefins) by multiple steps, hydroformylation makes these surfactants difficult to exhibit properties. As shown in Examples 1 to 3 of Table 1 of U.S. Patent No. 6,053,099, NMR properties indicate that a single dimerized alcohol product typically has multiple components and is branched. The distribution of types (methyl, ethyl, propyl, butyl, and higher) is broad, indicating that the branches have various attachment sites on the chain. It has also been shown that the degree of methyl branching (14-20%) and ethyl branching (13-16%) is high.

Patent Document 13 discloses a laundry detergent in combination with C ₁₆ Guerbet alcohol sulfates and alcohol ethoxylates. Compared to similar fully formulated detergent using linear C ₁₆ alcohol sulfates, detergent containing Guerbet alcohol sulfates, hot water (60 ° C.) and good wash in warm water (40 ° C.) I will provide a. Laundry using cold water (less than 30 ° C.) is neither disclosed nor suggested.

  U.S. Patent No. 6,057,031 teaches a laundry detergent composition made by dimerizing an even number of alpha olefins to produce vinylidene, hydroformylating the vinylidene to give an alcohol mixture, and sulfating the alcohol. Yes. Hydroformylation is carried out in an effective manner to provide an alcohol mixture in which methyl branched products are predominant. According to the application, methyl branched on an even number of carbons in the alkyl chain is believed to contribute to the rapid biodegradation of sulfate surfactants made from alcohols. Compared to similar sulfates with random branches on the chain, those branched on an even number of carbons had the same cleaning ability at 20 ° C, but improved biodegradability. It was.

  The use of enzymes containing lipases in laundry detergents is known. Lipases are believed to be effective in removing greasy soils. This is because the enzyme targets the degradation of fats such as fats and oils. Although lipase may improve cleaning performance, which combination of lipase and conventional surfactant will provide a synergistic improvement in cleaning performance, especially when employing cold water laundry. Still unpredictable.

US Pat. No. 6,020,303 US Pat. No. 6,060,443 US Pat. No. 6,153,577 US Pat. No. 6,320,080 International Publication No. 95/16016 European Patent Application No. 0693549 US Pat. No. 5,478,500 US Pat. No. 6,017,873 US Pat. No. 5,389,277 US Pat. No. 8,334,323 Japanese Patent No. 0215698 US Patent No. 6222077 International Publication No. 01/14507 International Publication No. 2013/181083

J. et al. Disp. Sci. Tech. 6 (1985) 223 SPEJ23 (1983) 913 J. et al. Chem. Soc. (1956) 579 J. et al. Chem. Soc. , Chem. Commun (1990) 711 Ind. Eng. Chem. 36 (1944) 610 J. et al. Am. Oil Chem. Soc. 44 (1967) 525 Varadaraj et al. , J .; Phys. Chem. 95 (1991), 1671, 1677, 1679, and 1682

  There is a continuing need for improved detergents, particularly laundry detergents that perform well in cold water. Of particular interest are detergents that can combat bacon stains or fat stains such as beef tallow. This is because these stains harden and adhere firmly to common fabric fibers. Ideally, the kind of cleaning performance in greasy soils that consumers naturally enjoy when using hot water can be achieved even with cold water.

  In one aspect, the present invention relates to a laundry detergent useful for cold water cleaning. The detergent comprises a lipase and a medium chain head group surfactant or an alkylene crosslinking surfactant.

The medium chain head group surfactant has a saturated or unsaturated, linear or branched C ₁₄ -C ₃₀ alkyl chain. Furthermore, the medium chain head group surfactant has a polar group (or “head group”) bonded to the central region carbon of the C ₁₄ -C ₃₀ alkyl chain. In some embodiments, the medium chain head group surfactant comprises alcohol sulfate, alcohol ethoxylate, ether sulfate, sulfonate, aryl sulfate, alcohol phosphate, amine oxide, quaternium, betaine and sulfone. Betaine.

The alkylene bridge surfactant is a saturated or unsaturated, and C ₁₂ -C ₁₈ alkyl chains or branched linear, and a polar group, the polar group and the central region of the C ₁₂ -C ₁₈ alkyl chain and a _C 1 -C ₂ alkylene group attached to the carbon. The alkylene cross-linking surfactant has a total of 14 to 19 carbons excluding the polar group. In some embodiments, the alkylene bridged surfactant is an alcohol sulfate, alcohol alkoxylate, ether sulfate, sulfonate, aryl sulfate, alcohol phosphate, amine oxide, quaternium, betaine and sulfobetaine. is there.

  In addition to either the medium chain head group surfactant or the alkylene crosslinking surfactant, the detergent comprises a lipase. Suitable lipases are derived from animals, plants, fungi, or microorganisms, and may be naturally derived or artificial mutants.

  Surprisingly, the inventors have found that when combined with a lipase, the detergents prepared using the medium chain head group surfactants or alkylene cross-linked surfactants efficiently liquefy fat stains at low temperatures. Provides outstanding cold water performance in removing fat stains such as bacon fat, butter, cooked heads, or beef tallow from soiled articles.

  In one aspect, the present invention relates to a lipase-containing detergent useful for cold water cleaning. Some of the detergents contain “medium chain head group” surfactants, while other detergents contain “alkylene bridged” surfactants. These two surfactant species are described in detail below.

(Lipase)
Surprisingly, the inventors have synergistically improved cleaning performance against greasy soil when lipase is used in combination with either a medium chain head group surfactant or an alkylene cross-linked surfactant (as described below). I found out.

  Lipase is an enzyme that exhibits a catalytic action to hydrolyze fats and oils into fatty acids and glycerol, monoglycerides and / or diglycerides. Suitable lipases for use herein include those derived from animals, plants, fungi, and microorganisms. Suitable lipase enzymes include forming layers, bark, plant roots and fruit seeds, oil palm, salad vegetables, rice, bran, barley and malt, wheat, oats and oat flour, cotton, oilseed rape, corn, millet, coconut , Walnut, fusarium, cannabis, and cucurbitaceae. In addition to naturally occurring lipases, chemically modified mutants or mutants produced by protein engineering can also be used.

  Suitable lipases include lipases from Humicola species (also referred to as Thermomyces) (for example, H. lanuginosa (disclosed in, for example, EP 258068 and 305216)). Lipase or H. insolens from T. lanuginosus (see, for example, WO 96/13580); Pseudomonas species lipase (for example, P. alkaligenes or P. pseudoalkigenes (eg, published European patent applications) No. 218272), P. cepacia (see, for example, EP-A-331376), P. stazzelli (see, for example, British Patent No. 1,372,034) , P. fluorescens, Pseudomonas species SD Strain 05 (see, eg, WO 95/06720 and 96/27002), or P. Wisconsinensis (see, eg, WO 96/122012); Lipases (for example, Bacillus subtilis, B. stearothermophilus, or B. pumilus (see, eg, WO 91/16422)).

  Lipase mutants can also be used. These variants are as disclosed in US Pat. Nos. 8,187,854, 7,396,657, and 6,156,552, the teachings of which are incorporated herein by reference. It is. Further lipase variants include WO 92/05249, 94/01541, 95/35381, 96/00292, 95/30744, 94/25578, 95/14783. Nos. 95/22615, 97/04079, and 97/070202, and European Patent Application Nos. 0407225 and 0260105.

  Suitable lipases include the trade names Lipex (TM), Lipolex (TM), Lopclean (TM), Lipolase (TM), Lipolase Ultra (TM), Lipopan (TM), Lipopan Xtra (TM), Lypozyme (TM), Included are those sold under the Palatase ™, Resinase ™, Novozym ™ 435, and Lipoprime ™, all of which are available from Novodimes. Another suitable lipase is available as Lipase P Amano ™ (manufactured by Amano Pharmaceuticals). Further suitable lipases are lipases such as M1 Lipase ™ and Lipomax ™ (DSM) and Lumafast ™ (Danisco). Preferred lipases include D96L lipolytic enzyme variants of natural lipase derived from Humicola lanuginosa as disclosed in US Pat. No. 6,017,871. It is preferable to use Humicola lanuginosa DSM4106 strain.

  The lipase can be used in any preferred amount. Generally, the lipase is present in the detergent of the present invention in an amount of 10-20000 LU / g, or even 100-10000 LU / g, relative to the detergent. The LU unit for lipase activity is defined in WO 99/42566. The amount of lipase in the wash solution is typically from 0.01 to 5 mg / L, more typically from 0.1 to 2 mg / L as the active lipase protein. As a weight percentage, the lipase can be used in the detergent at 0.00001-2% by weight, usually 0.0001-1% by weight, or 0.001-0.5% by weight. Even can be used.

  The lipase may be contained in the detergent in any easy-to-handle form. For example, it may be included in the detergent in the form of undusted granules, stabilizing liquid, or protective (eg coated) particles.

  Additional examples of lipases useful and suitable herein include US Pat. Nos. 5,069,810, 5,093,256, 5,153,135, 5,614,484, 5,763,383, 6,177,010. No. 6,869,033, No. 7,790,666, No. 8,891,743, and No. 8,859,480, and U.S. Patent Application Publication No. 2011/0212877. These teachings are incorporated herein by reference.

(Medium chain head group surfactant)
“Medium chain head group” surfactant means a surfactant in which the polar group is located at or near the center of the longest continuous alkyl chain. The medium chain head group surfactant is bonded to a saturated or unsaturated, linear or branched C ₁₄ -C ₃₀ alkyl chain and carbon in the central region of the C ₁₄ -C ₃₀ alkyl chain. And having a polar group.

The “central carbon” of the C ₁₄ -C ₃₀ alkyl chain is (1) finding the longest continuous alkyl chain, (2) counting the number of carbons in the chain, (3) in the longest chain. Revealed by dividing the number of carbons by two. If the longest continuous carbon chain has an even number of carbons, the central carbon is found by counting the results in (3) from either chain end. In this case, there are two positions that can be combined. If the longest continuous carbon chain has an odd number of carbons, the result in (3) is rounded up to the next largest integer value and the central carbon is counted from any chain end. Can be found by There is only one position that can be combined.

As an example, consider sodium 9-octadecyl sulfate. The longest continuous carbon chain has 18 carbons. Divide 18 by 2 to get 9. Counting the 9th carbon from either end and attaching the polar group gives the same result from either end because there is no branch in the _C18 chain.

  As another example, consider sodium 2-methyl-8-pentadecyl sulfate. The longest continuous carbon chain has 15 carbons. Dividing 15 by 2 gives 7.5. After rounding up 7.5 to 8, the 8th carbon from either end is counted and the polar group is attached.

  “Central region carbon” means “central carbon” as defined above or carbon that is in close proximity to the central carbon. When the longest continuous alkyl chain has an even number of carbons, the two central carbons and any central carbon in the α- or β-position relative to any central carbon are within the “central region”. There will be. When the longest continuous alkyl group chain has an odd number of carbons, the central carbon and any carbon in the α-, β-, or γ-position to the central carbon are within the “central region” It will be.

  Another method for identifying the central region carbon is as follows. Let N be the number of carbons in the longest continuous alkyl chain. N is a value of 14-30. When N is even, the central region carbon is found by counting the N / 2, (N / 2) -1, or (N / 2) -2 carbons from either end of the chain. . When N is an odd number, the central region carbon is (N + 1) / 2, [(N + 1) / 2] -1, [(N + 1) / 2] -2, or [( N + 1) / 2] —found by counting the third carbon.

  As an example, if N = 25, the central region carbon will be found by counting the 13, 12, 11, or 10th carbon from either end of the chain. If N = 18, the central region carbon will be found by counting the ninth, eighth, or seventh carbon from either end of the chain.

  Based on the above considerations, a detergent considered within the scope of the present invention will include a medium chain head group surfactant having one or more of the following structures. 14-7, 14-6, 14-5, 15-8, 15-7, 15-6, 15-5, 16-8, 16-7, 16-6, 17-9, 17-8, 17-7, 17-6, 18-9, 18-8, 18-7, 19-10, 19-9, 19-8, 19-7, 20-10, 20-9, 20-8, 21- 11, 21-10, 21-9, 21-8, 22-11, 22-10, 22-9, 23-12, 23-11, 23-10, 23-9, 24-12, 24-11, 24-10, 25-13, 25-12, 25-11, 25-10, 26-13, 26-12, 26-11, 27-14, 27-13, 27-12, 27-11, 28- 14, 28-13, 28-12, 29-15, 29-14, 29-13, 29-12, 30-15, 30-14, and 30-1 It is. Here, the first number is N, that is, the carbon number in the longest continuous alkyl chain, and the second number is the position of the polar group with respect to the carbon number from one end of the alkyl chain.

The medium chain head group surfactant has a saturated or unsaturated, linear or branched C ₁₄ -C ₃₀ alkyl chain, preferably a C ₁₄ -C ₂₀ alkyl chain, and more preferably _has a C 14 _{-C 18} alkyl chains.

  In the medium-chain head group surfactant in which the longest continuous alkyl chain has an even number of carbons, the polar group is a carbon in the α-position with respect to one or any of the two central carbons. It is preferable that it is combined with. More preferably, the polar group is bonded to one of the central carbons.

  In medium chain head group surfactants where the longest continuous alkyl group has an odd number of carbons, the polar group is bound to the central carbon or a carbon in the α- or β-position relative to the central carbon. And preferred. More preferably, the polar group is bonded to the central carbon or the α-position carbon with respect to the central carbon. Optimally, the polar group is attached to the central carbon.

  Since the position on the chain is believed to be more important than the nature of the polar group, various polar groups are considered suitable for use. Therefore, suitable medium chain head group surfactants include alcohol sulfate, alcohol ethoxylate, ether sulfate, sulfonate, aryl sulfonate, alcohol phosphate, amine oxide, quaternium, betaine, sulfobetaine. , And the like, and mixtures thereof. Alcohol sulfates, ether sulfates, and sulfonates are particularly preferred medium chain head group surfactants.

  Alcohol sulfates are readily made according to known methods by reacting the corresponding alcohol with a sulfiding agent (see, eg, US Pat. No. 3,544,613, the teachings of which are hereby incorporated by reference). Incorporated into). Sulfamic acid is an easy-to-use drug that sulphates hydroxyl groups without disturbing any unsaturated moieties present in the alkyl chain. Thus, if desired, the desired alkyl ammonium sulfate is readily provided by warming the alcohol with sulfamic acid under conditions where urea or other proton acceptors are present. The ammonium sulfate is readily converted to an alkali metal sulfate by reaction with an alkali metal hydroxide (eg, sodium hydroxide) or other ion exchange agent (see the preparation of sodium 9-octadecyl sulfate below). Converted to Other suitable sulfurizing agents include sulfur trioxide, fuming sulfuric acid, and chlorosulfonic acid, which may be used.

  Sulfate alcohol precursors may be purchased or synthesized. If the medium chain alcohol is not commercially available, the alcohol can be prepared from aldehydes, alkyl halides, and magnesium using known Grignard reactions. Forming an internal olefin by metathesis, then reacting the internal olefin with sulfuric acid under cold conditions, and performing either cold neutralization of the resulting sulfate or hydrolysis of the sulfate ester with warm water There are other ways.

  If an alcohol ethoxylate is desired, the alcohol precursor is usually reacted with ethylene oxide in the presence of a base to add the desired average number of oxyethylene units. Typically, the number of oxyethylene units is in the range of 0.5-100, preferably in the range of 1-30, more preferably in the range of 1-10.

  If an ether sulfate is desired, the alcohol precursor is first alkoxylated by reacting the alcohol precursor with ethylene oxide, propylene oxide, or a combination thereof to produce an alkoxylate. Alkoxylation is usually catalyzed by a base (eg, KOH), but other catalysts such as double metal cyanide complexes (see, eg, US Pat. No. 5,482,908) may also be used. it can. The oxyalkylene units may be included randomly or in blocks. Sulfation of an alcohol alkoxylate (usually an alcohol ethoxylate) provides the desired ether sulfate.

  Suitable aliphatic alcohol precursors for the medium chain sulfate or ether sulfate include, for example, 7-tetradecanol, 6-tetradecanol, 5-tetradecanol, 8-pentadecanol, 7-pentadecanol. Nord, 6-Pentadecanol, 5-Pentadecanol, 8-Hexadecanol, 7-Hexadecanol, 6-Hexadecanol, 9-Septadecanol, 8-Septadecanol, 7-Septadecanol, 6-septadecanol, 9-octadecanol, 8-octadecanol, 7-octadecanol, 10-nonadecanol, 9-nonadecanol, 8-nonadecanol, 7-nonadecanol, 10-eicosanol, 9-eicosanol, 8- Eicosanol, 11-hen eicosanol, 10-hen eicosanol, 9-hen eicosano 8-heneicosanol, 11-docosanol, 10-docosanol, 9-docosanol, 12-tricosanol, 11-tricosanol, 10-tricosanol, 9-tricosanol, 12-tetracosanol, 11-tetracosanol, 10- Tetracosanol, 9-tetracosanol, 13-pentacosanol, 12-pentacosanol, 11-pentacosanol, 10-pentacosanol, 13-hexacosanol, 12-hexacosanol, 11-hexacosanol , 14-heptacosanol, 13-heptacosanol, 12-heptacosanol, 11-heptacosanol, 14-octacosanol, 13-octacosanol, 12-octacosanol, 15-nonacosanol, 14-nonacosanol, 13-nonacosanol 12 nonacosanol, 15 triacontanol, 14-triacontanol, 13-triacontanol and the like thereto, and mixtures thereof. 9-octadecanol and 8-hexadecanol are particularly preferred.

Medium chain sulfonates can be made by reacting internal olefins with sulfonating agents. Sulfonation is carried out using known methods including reacting the olefin with sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid, or other known sulfonating agents. Chlorosulfonic acid is a preferred sulfonating agent. The sultone, the direct product of the reaction of olefins with SO ₃ , chlorosulfonic acid, and the like, is then subjected to hydrolysis and neutralization with an aqueous caustic to produce alkene sulfonates and Mixtures of hydroxyalkene sulfonates may be provided. Suitable methods for sulfonating olefins are disclosed in U.S. Pat. Nos. 3,169,142, 4,148,821 and U.S. Published Application 2010/0282467. These teachings are incorporated herein by reference.

  Suitable medium chain sulfonates can be made by sulfonating internal olefins. Preferred internal olefins include, for example, 7-tetradecene, 6-tetradecene, 5-tetradecene, 8-pentadecene, 7-pentadecene, 6-pentadecene, 5-pentadecene, 8-hexadecene, 7-hexadecene, 6-hexadecene, 9- Septadecene, 8-Septadedecene, 7-Septadedecene, 6-Septadedecene, 9-Octadecene, 8-Octadecene, 7-Octadecene, 10-Nonadecene, 9-Nonadecene, 8-Nonadecene, 7-Nonadecene, 10-Eicosene, 9-Eicosene, 8-eicosene, 11-heneicosene, 10-heneicosene, 9-heneicosene, 8-heneicosene, 11-docosene, 10-docosene, 9-docosene, 12-tricosene, 11-tricosene, 10-tricosene, 9-tricosene, 12- Te Lacocene, 11-tetracocene, 10-tetracocene, 13-pentacocene, 12-pentacocene, 11-pentacocene, 10-pentacocene, 13-hexacocene, 12-hexacocene, 11-hexacocene, 14-heptacocene, 13-heptacocene, 12-heptacocene, 11-heptacocene, 14-octacocene, 13-octacocene, 12-octacocene, 15-nonacocene, 14-nonacocene, 13-nonacocene, 12-nonacocene, 15-triacontane, 14-triacontane, 13-triacontane, and these A mixture is included.

  The internal olefin precursor of the medium chain sulfonate may be olefin metathesis (and subsequent fractionation), alcohol dehydration, thermal decomposition, elimination reaction, Wittig reaction (for example, Angew. Chem., Int. Ed. Engl. 4 (1965) 830; Tetrahedron Lett. 26 (1985) 307; and U.S. Pat. No. 4,642,364), and other synthetic methods known to those skilled in the art. For further examples of suitable methods, see I.I. Harrison and S.H. Harrison, Compendium of Organic Synthetic Methods, Vol. 1 (1971) (Wiley) and references cited therein.

  Medium chain aryl sulfonates can be made by alkylating an arene, such as benzene, toluene, xylene, or the like, with an internal olefin followed by sulfonation and neutralization of the aromatic ring.

  The alcohol precursor of the medium chain head group surfactant can be converted to the corresponding amine by an amination process. In some instances, it may be more desirable to make the amine via an intermediate such as a halide or other compound having a good leaving group.

  The medium chain amine oxide and quaternium can be easily obtained from the corresponding tert-amine by oxidation or quaternization. The medium chain betaine and sulfobetaine can be prepared, for example, by reaction with sodium monochloroacetate (betaine) or by reaction with sodium pyrosulfite and epichlorohydrin in the presence of a base (sulfobetaine). Can be easily obtained from For examples of methods for preparing quarternium, betaine, and sulfobetaine, see WO 2012/061098. This teaching is incorporated herein by reference.

(Alkylene cross-linking surfactant)
In some embodiments, the detergent comprises an “alkylene bridged” surfactant. The surfactant comprises (a) a saturated or unsaturated, linear or branched C ₁₂ -C ₁₈ alkyl chain, (b) a polar group, (c) the polar group and the C ₁₂ and a _C 1 -C ₂ alkylene group which is bonded to the central area of carbon atoms in -C ₁₈ alkyl chains. Excluding the polar group, the surfactant has 14 to 19 carbons in total, preferably 15 to 19 carbons, and preferably 16 to 18 carbons. More preferred.

“Alkylene cross-linking surfactant” means that the polar group is bonded to a C ₁ -C ₂ alkylene bridge, and the cross-linking is the center of the longest continuous alkyl chain (excluding the C ₁ -C ₂ alkylene group). It means a surfactant bonded to carbon located at or near the center.

The “central carbon” of a C ₁₂ -C ₁₈ alkyl chain is (1) finding the longest continuous alkyl chain excluding the C ₁ -C ₂ alkylene group, (2) counting the number of carbons in the chain, (3) Revealed by dividing the number of carbons in the longest chain by two. If the longest continuous carbon chain (excluding C ₁ -C ₂ alkylene groups) has an even number of carbons, the central carbon is found by counting the answers in (3) from either chain end. In this case, there are two bondable positions for the alkylene bridge. When the longest continuous carbon chain (excluding C ₁ -C ₂ alkylene groups) has an odd number of carbons, the result in (3) is rounded up to the next largest integer value, and the central carbon is either It can be found by counting the rounded answers from the chain ends. There is only one position that can be combined.

As an example, consider sodium 2-hexyl-1-undecyl sulfate. The longest continuous carbon chain (-CH ₂ - except for the bridge) has a 16 carbons. Divide 16 by 2 to get 8. Count the 8th carbon from either end and position one of the two central carbons.

As another example, consider sodium 2-octyl-1-decyl sulfate. The longest continuous carbon chain (excluding —CH ₂ —bridges) has 17 carbons. Dividing 17 by 2 gives 8.5. Round 8.5 to 9 Counting the ninth carbon from either end provides a unique central carbon position.

“Central region carbon” means “central carbon” as defined above or carbon in close proximity to said central carbon. If the alkyl chain of consecutive said longest has an even number of carbon (excluding C ₁ -C ₂ alkylene group), in α- or β- position with respect to the two central carbon and any central carbon Any carbon will be in the “central region”. When the longest continuous alkyl chain has an odd number of carbons (excluding C ₁ -C ₂ alkylene groups), any in the α-, β-, or γ-positions relative to the central carbon and the central carbon Of carbon is in the “central region”.

Another method for identifying the central region carbon is as follows. N is said the longest continuous carbon atoms in the alkyl chain (excluding C ₁ -C ₂ alkylene group). N is a value of 12-18. When N is even, the central region carbon is found by counting the N / 2, (N / 2) -1, or (N / 2) -2 carbons from either end of the chain. . When N is an odd number, the central region carbon is (N + 1) / 2, [(N + 1) / 2] -1, [(N + 1) / 2] -2, or [( N + 1) / 2] —found by counting the third carbon.

  As an example, if N = 15, the carbon in the central region will be found by counting the 8, 7, 6, or 5th carbon from either end of the chain. If N = 18, the carbon in the central region will be found by counting the 9, 8, or 7th carbon from either end of the chain.

Based on the above idea, a detergent considered within the scope of the present invention will include an alkylene cross-linked surfactant having one or more of the following structures. That is, 12-6, 12-5, 12-4, 13-7, 13-6, 13-5, 13-4, 14-7, 14-6, 14-5, 15-8, 15-7, 15-6, 15-5, 16-8, 16-7, 16-6, 17-9, 17-8, 17-7, 17-6, 18-9, 18-8, and 18-7. . Here, the number of first is N, that is, the number of carbon atoms in contiguous alkyl chain of the longest (excluding C ₁ -C ₂ alkylene group), the second number, from one end of the alkyl chain It is the position of the alkylene bridging polar group with respect to the carbon number.

In the case of an alkylene bridged surfactant in which the longest continuous alkyl group has an even number of carbon atoms (excluding C ₁ -C ₂ alkylene groups), the alkylene bridge is either one of the two central carbons. Or it is preferable when it couple | bonds with the carbon which exists in alpha-position with respect to any central carbon. More preferably, the alkylene bridge is bonded to one of the two central carbons.

For alkylene bridge surfactants the longest consecutive alkyl group having an odd number of carbon atoms (excluding C ₁ -C ₂ alkylene group), the alkylene bridge is to the central carbon or the central carbon α- Alternatively, it is preferably bonded to carbon in the β-position. More preferably, the alkylene bridge is bonded to the central carbon or carbon in the α-position with respect to the central carbon. Optimally, the alkylene bridge is bonded to the central carbon.

  Since the position on the chain is believed to be more important than the nature of the polar group, various polar groups are considered suitable for use. Therefore, suitable alkylene cross-linking surfactants include alcohol sulfates, alcohol alkoxylates, ether sulfates, sulfonates, aryl sulfonates, alcohol phosphates, amine oxides, quaternium, betaine, sulfobetaine, and The like, as well as mixtures thereof, are included. Alcohol sulfates, ether sulfates, and sulfonates are particularly preferred medium chain head group surfactants.

Sulfate and ether sulfate alcohol precursors may be purchased or synthesized. Suitable gerbet alcohols are those having a —CH ₂ — “crosslink” at the hydroxyl group, but Sasol (ISOFOL® alcohol), BASF (eg, Euthanol® alcohol), Commercially available from Lubrizol and other suppliers. Commercially available examples include 2-butyl-1-decanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-hexyl-1-dodecanol, and the like. Suitable gerbet alcohol may be synthesized. In a classic synthetic approach, the gerbet alcohol reacts with 2 moles of aliphatic alcohol at high temperature in the presence of a suitable catalyst to induce alcohol oxidation to the aldehyde, aldol condensation, dehydration, and hydrogenation. And may be made by providing the resulting garbed product. Suitable catalysts include, among others, nickel salts, lead salts (eg, US Pat. No. 3,119,880), copper oxide, lead oxide, zinc oxide, and other metal oxides (US Pat. No. 3,558,716), Or palladium and silver compounds (see, for example, US Pat. No. 3,979,466 or US Pat. No. 3,864,407). The reaction of 2 moles of 1-octanol to give 2-hexyl-1-decanol is shown below.

  Methylene bridged alcohols that are similar to gerbet alcohol and suitable for use herein are preferably catalysts that prevent or minimize the degree of isomerization of carbon-carbon double bonds. , Frankel, J. Am. Oil. Chem. Soc. 48 (1971) 248), may be used for the hydroformylation of internal olefins. Internal olefins can be made in a number of ways including, for example, self-metathesis of α-olefins. The synthesis of 2-hexyl-1-nonanol from 1-octane is shown by the following approach.

  Suitable methylene bridged alcohols for use may be made in a multi-step synthesis starting from an aldehyde. The aldehyde is converted to an imine (eg, using cyclohexylamine), deprotonated, alkylated, deprotected and then reduced to give the desired alcohol. An example of the synthesis of 2-heptyl-1-decanol from nonal and 1-bromooctane is shown below. The synthesis is described in detail in the experimental section.

  Suitable methylene bridged alcohols for use may be made by hydroboration of vinylidene produced by dimerizing α-olefins. Both the olefin dimerization reaction and the hydroboration / oxidation step are highly selective. The olefin dimerization step to produce the vinylidene is performed using an alkylaluminum compound (US Pat. Nos. 3,957,664, 4,973,788, 5,625,105, 5,659,100, 6566319). , And references referenced herein, the teachings of which are incorporated herein by reference), metallocene / alumoxane mixtures (see, for example, US Pat. No. 4,658,078). Or may be catalyzed by the like. Hydroboration and oxidation are initiated with diborane to give the primary alcohol with almost no exception (HC Brown, Hydroboratio (1962) WA Benjamin, pp. 12-13, 114-115. See). The preparation of 2-hexyl-1-decanol from 1-octane represents the following approach.

Vinylidene may be used to make dimethylene (—CH ₂ CH ₂ —) crosslinked alcohols. Dimethylene bridged alcohols may be made, for example, by hydroformylation of vinylidene using a catalyst that minimizes isomerization and formation of methyl branched isomers. Although methyl branching is believed to be advantageous for enhancing biodegradability (see WO 2013/181283), the purpose herein is to form a product with a medium chain polar group. To maximize other products, including methyl-branched hydroformylation products. Suitable hydroformylation catalysts and reaction conditions for selectively adding CO to the vinylidene terminus are disclosed in GB-A-2451325 and U.S. Pat. Nos. 3,952,068 and 3,887,624. . These teachings are incorporated herein by reference. Examples are as follows.

  Dimethylene bridged alcohol can be obtained by simply heating vinylidene with paraformaldehyde and then catalytically hydrogenating the resulting allyl alcohol mixture according to the method taught by Kashimura et al. (JP 2005-298443). Can also be made.

  Alcohol sulfates are readily made according to known methods by reacting the corresponding alkylene bridged alcohol with a sulfite agent (eg, US Pat. No. 3,544,613, the teachings of which are hereby incorporated by reference). Incorporated into the book.) Sulfamic acid is an easy-to-use agent that sulphates hydroxyl groups without disturbing any unsaturated moieties present in the alkyl chain. Thus, the desired alkyl ammonium sulfate is readily provided by warming the alcohol with sulfamic acid, optionally in the presence of urea or other proton acceptors. Ammonium sulfate is converted to alkali metal sulfate by reaction with an alkali metal hydroxide (eg, sodium hydroxide) or other ion exchange reagent (see the preparation of sodium 2-hexyl-1-decyl sulfate below). Easily converted to salt. Other suitable sulfite agents include sulfur trioxide, fuming sulfuric acid, and chlorosulfonic acid.

  If an alcohol alkoxylate is desired, the alcohol precursor is usually a base (eg, KOH), double metal cyanide (DMC) complex (eg, US Pat. No. 5,482,908) to add the desired average number of oxyalkylene units. In the presence of other catalysts, or in the presence of ethylene oxide, propylene oxide, butylene oxide, or the like, or mixtures thereof. Ethylene oxide is particularly preferred. Typically, the number of oxyalkylene units is in the range of 0.5-100, preferably in the range of 1-30, and more preferably in the range of 1-10.

  If an ether sulfate is desired, the alcohol precursor is first alkoxylated as described above. Sulfation of an alcohol alkoxylate (usually an alcohol ethoxylate) provides the desired ether sulfate.

In one aspect, the alkylene crosslinking surfactant is an alcohol sulfate, alcohol alkoxylate, or ether sulfate of a C ₁₄ aliphatic alcohol. Preferred alcohols in this group include, for example, 2-hexyl-1-octanol, 2-pentyl-1-nonanol, 2-butyl-1-decanol, 2-propyl-1-undecanol, 3-pentyl-1-nonanol, 3-butyl-1-decanol, 3-propyl-1-undecanol, and mixtures thereof are included.

In another embodiment, an alkylene bridge surfactants are C ₁₅ alcohol sulfates of fatty alcohols, alcohol alkoxylates, or ether sulfates. Preferred alcohols in this group include, for example, 2-hexyl-1-nonanol, 2-pentyl-1-decanol, 2-butyl-1-undecanol, 3-hexyl-1-nonanol, 3-pentyl-1-decanol, 3-butyl-1-undecanol, 3-propyl-1-dodecanol, and mixtures thereof are included.

In another embodiment, an alkylene bridge surfactants are C ₁₆ fatty alcohol sulfates of alcohols, alcohol ethoxylates, or ether sulfates. Preferred alcohols in this group include, for example, 2-heptyl-1-nonanol, 2-hexyl-1-decanol, 2-pentyl-1-undecanol, 2-butyl-1-dodecanol, 3-hexyl-1-decanol, 3-pentyl-1-undecanol, 3-butyl-1-dodecanol, and mixtures thereof are included.

In another embodiment, an alkylene bridge surfactants are C ₁₇ alcohol sulfates of fatty alcohols, alcohol alkoxylates, or ether sulfates. Preferred alcohols in this group include, for example, 2-heptyl-1-decanol, 2-hexyl-1-undecanol, 2-pentyl-1-dodecanol, 3-heptyl-1-decanol, 3-hexyl-1-undecanol, 3-pentyl-1-dodecanol, 3-butyl-1-tridecanol, and mixtures thereof are included.

In another aspect, the alkylene bridged surfactant is an alcohol sulfate, alcohol alkoxylate, or ether sulfate of a _C18 aliphatic alcohol. Preferred alcohols in this group include, for example, 2-octyl-1-decanol, 2-heptyl-1-undecanol, 2-hexyl-1-dodecanol, 2-pentyl-1-tridecanol, 3-heptyl-1-undecanol, 3-hexyl-1-dodecanol, 3-pentyl-1-tridecanol, and mixtures thereof are included.

In yet another aspect, the alkylene bridged surfactant is an alcohol sulfate, alcohol alkoxylate, or ether sulfate of a C ₁₉ aliphatic alcohol. Preferred alcohols in this group include, for example, 2-octyl-1-undecanol, 2-heptyl-1-dodecanol, 2-hexyl-1-tridecanol, 3-octyl-1-undecanol, 3-heptyl-1-dodecanol, 3-hexyl-1-tridecanol, 3-pentyl-1-tetradecanol, and mixtures thereof are included.

In another preferred embodiment, the alkylene bridged surfactant is a C ₁ -C ₂ alkylene group bonded to the central region carbon of a C ₁₂ -C ₁₈ alkyl chain and a C ₁₂ -C ₁₈ alkyl chain in addition to a polar group. Containing C ₁₄ -C ₁₉ alkyl moieties. Preferred C ₁₄ alkyl moieties include, for example, 2-hexyl-1-octyl, 2-pentyl-1-nonyl, 2-butyl-1-decyl, 2-propyl-1-undecyl, 3-pentyl-1-nonyl, 3-butyl-1-decyl and 3-propyl-1-undecyl are included. Preferred _{C 15} alkyl moiety, for example, 2-hexyl-1-nonyl, 2-pentyl-1-decyl, 2-butyl-1-undecyl, 3-hexyl-1-nonyl, 3-pentyl-1-decyl, 3-butyl-1-undecyl and 3-propyl-1-dodecyl are included. Preferred _{C 16} alkyl moiety, for example, 2-heptyl-1-nonyl, 2-hexyl-1-decyl, 2-pentyl-1-undecyl, 2-butyl-1-dodecyl, 3-hexyl-1-decyl, 3-pentyl-1-undecyl and 3-butyl-1-dodecyl are included. Preferred C ₁₇ alkyl moieties include, for example, 2-heptyl-1-decyl, 2-hexyl-1-undecyl, 2-pentyl-1-dodecyl, 3-heptyl-1-dodecyl, 3-hexyl-1-undecyl, 3-pentyl-1-decyl and 3-butyl-1-dodecyl are included. Preferred _C18 alkyl moieties include, for example, 2-octyl-1-decyl, 2-heptyl-1-undecyl, 2-hexyl-1-dodecyl, 2-pentyl-1-tridecyl, 3-heptyl-1-undecyl, 3-hexyl-1-dodecyl and 3-pentyl-1-tridecyl are included. Preferred C ₁₉ alkyl moieties include, for example, 2-octyl-1-undecyl, 2-heptyl-1-dodecyl, 2-hexyl-1-tridecyl, 3-octyl-1-undecyl, 3-heptyl-1-dodecyl, 3-hexyl-1-tridecyl and 3-pentyl-1-tetradecyl are included.

Preferred sulfonates may be made by reacting an olefin with a sulfonating or sulfurizing agent. The unsaturated part in the olefin is preferably in the C ₁ -C ₂ branching group. For example, the vinylidene described above has an unsaturated moiety in the C ₁ branching group. Suitable olefins having unsaturation in C ₂ branching groups, after hydroformylation vinylidene can be made by dehydrating the alcohol product.

Sulfonation is carried out using known methods including reacting olefins with sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid, or other known sulfonating agents. Chlorosulfonic acid is a preferred sulfonating agent. The sultone, the direct product of the reaction of olefins with SO ₃ , chlorosulfonic acid, and the like, is then subjected to hydrolysis and neutralization with an aqueous caustic to produce alkene sulfate and hydroxy A mixture of alkene sulfates is provided. Suitable methods for sulfonating olefins are disclosed in US Pat. No. 3,169,142, US Pat. No. 4,148,882 and US 2010/0282467. These teachings are incorporated herein by reference. As mentioned above, vinylidene may be used as an initiator for sulfonation. For example, GB 1139158 teaches that 2-hexyl-1-decene is sulfonated to produce a product containing mostly alkene sulfonates.

  Sulphiteation is accomplished by combining the olefin with at least an equimolar amount of sulfite agent in water (and usually a co-solvent such as isopropanol) using known methods. Suitable sulfite agents include, for example, sodium sulfite, sodium bissulfite, sodium metabissulfite, or the like. Optionally, a catalyst or initiator such as peroxide, iron, or other free radical initiator is included. Typically, the reaction is carried out at 15-100 ° C. until reasonably complete. Methods for sulfite olefins can be found in US Pat. Nos. 2,653,970, 4,087,457, and 4,275,031. These teachings are incorporated herein by reference.

Olefin sulfonation or sulfite may provide a reaction product comprising one or more alkane sulfonates, alkene sulfonates, sultone, and hydroxyl-substituted alkane sulfonates. The following scheme shows hydroxyl substituted alkane sulfonates and alkene sulfonates that can be generated from sulfonation of C ₂ -branched olefins.

Alkylene bridged aryl sulfonates can be prepared by alkylating arenes such as benzene, toluene, xylene, or the like with vinylidene or other olefins having an unsaturated moiety within the C ₁ -C ₂ branching group, and then fragrance. It can be made by sulfonating and neutralizing the ring.

  Suitable alcohol phosphates can be made by reacting alcohol precursors or the above alcohol alkoxylates with phosphoric anhydride, polyphosphoric acid, or the like, or mixtures thereof according to known methods. For example, D.D. Tracy et al. , J .; Surf. Det. 5 (2002) 169, and U.S. Pat. Nos. 6,666,408, 5,463,101, and 5,550,274. These teachings are incorporated herein by reference.

  The alcohol precursor of the above-described alkylene cross-linking surfactant may be converted to the corresponding primary, secondary, or tertiary amine by an amination process. In some situations it may be more preferable to make the amine via an intermediate such as a halide or other compound with a good leaving group. The amination is preferably carried out in a single step by reacting the corresponding aliphatic alcohol with ammonia or a primary or secondary amine in the presence of an amination catalyst. Suitable amination catalysts are known. Catalysts containing copper, nickel, and / or alkaline earth metal compounds are common. See US Pat. Nos. 5,696,294, 4,994,622, 4,594,455, 4,409,399, and 3,497,555 for suitable catalysts and processes for amination. These teachings are incorporated herein by reference.

  Alkylene bridged amine oxides and quaternium can be readily obtained from the corresponding tert-amine by oxidation or quaternization. Alkylene-bridged betaines and sulfobetaines are easily obtained from the corresponding tert-amine, for example by reaction with sodium monochloroacetate (betaine) or by reaction with sodium pyrosulfite and epichlorohydrin in the presence of a base (sulfobetaine). Can get to. See WO 2012/061098 for examples of methods for preparing quarternium, betaine, and sulfobetaine. This teaching is incorporated herein by reference. An example of the procedure is as follows.

(Cold water cleaning)
In another aspect, the present invention relates to a cold water cleaning method using a laundry detergent comprising a lipase and either the above medium chain head group surfactant or an alkylene cross-linked surfactant.

  “Cold water” means water at a temperature below 30 ° C., preferably 5 ° C. to 28 ° C., more preferably 8 ° C. to 25 ° C. According to the climate, the original water will have a temperature in this range without the need for heat.

  Preferably, the detergent comprises lipase and water plus medium chain head group surfactant or alkylene cross-linked surfactant. The amount of water present may vary widely, but usually depends on the intended use, the form in which the detergent is supplied, the desired level of activity, and other factors. In actual use, it will usually be diluted with a small, large or very large proportion of water, depending on the equipment available for cleaning. In general, the amount of water used will be an amount effective to provide 0.001 to 5 weight percent active surfactant in the wash.

  Preferred detergents contain 1 to 20% by weight, more preferably 2 to 15% by weight (based on 100% active) of medium chain head group surfactants or alkylene cross-linked surfactants.

  In addition to the medium chain head group surfactant or the alkylene cross-linked surfactant, the detergent used in the cold water cleaning method may contain an alkyl branched surfactant component in a proportion. It is preferred that the detergent contains at most a portion of the alkyl crosslinking component. In one aspect, the medium chain head group surfactant or alkylene bridged surfactant has some methyl or ethyl branching on the longest continuous alkyl chain or on the alkylene bridge. In a preferred embodiment, at least 50 mol%, more preferably at least 70 mol% of the medium chain head group surfactant or alkylene crosslinking surfactant is substantially free of methyl or ethyl branches.

  The detergent of the present invention provides improved cold water cleaning performance. To measure the soil removal index (SRI), it is common in the art to wash a stained swatch under carefully controlled conditions. Details of the procedure will be apparent in the experimental section below. Compared to the soil removal index provided by similar detergents with medium chain head group surfactants or alkylene cross-linked surfactants but without lipases, the lipase-containing detergents of the present invention have at least one oil stain. An improvement in soil removal index of at least 1.0 unit, preferably at least 2.0 units, is provided at the same wash temperature of less than 30 ° C. Fat stains include, for example, bacon fat, beef tallow, butter, cooked heads, solid oils, vegetable waxes, petroleum waxes, and the like. On the SRI scale, a difference of 0.5 units can be distinguished with the naked eye.

  In certain preferred embodiments, the detergent composition further comprises a nonionic surfactant. The nonionic surfactant is preferably an aliphatic alcohol ethoxylate.

  In other preferred embodiments, the detergent further comprises an anionic surfactant. The anionic surfactant is preferably one selected from linear alkylbenzene sulfonates, aliphatic alcohol ethoxylate sulfates, aliphatic alcohol sulfates, and mixtures thereof.

  In another preferred embodiment, the detergent is in the form of a liquid, powder, paste, granule, tablet, or molded solid, or a water soluble sheet, sachet or pod.

  In another preferred embodiment, the detergent further comprises water, an aliphatic alcohol ethoxylate, and an anionic surfactant selected from linear alkyl benzene sulfate, aliphatic alcohol ethoxylate sulfate, and aliphatic alcohol sulfate. It is out.

  In another preferred embodiment, the detergent comprises 5-15% by weight aliphatic alcohol ethoxylate, 1-20% by weight medium chain head group surfactant or alkylene cross-linked surfactant, linear alkyl benzene sulfate, fat 5 to 15% by weight of an anionic surfactant selected from aliphatic alcohol ethoxylate sulfate and aliphatic alcohol sulfate.

  In one aspect, the detergent may comprise a medium chain head group surfactant or an alkylene crosslinking surfactant, water, solvent, hydrotrope, cosurfactant, or mixtures thereof. The solvent and / or co-surfactant and hydrotrope typically serve to compatibilize the mixture of water and medium chain head group surfactant or alkylene cross-linked surfactant. “Incompatible” mixtures of water and medium chain head group surfactants or alkylene cross-linked surfactants (without solvent and / or auxiliary) are opaque at temperatures of about 15 ° C. to 25 ° C. This product form is difficult to ship and difficult to formulate into commercial detergent formulations. In contrast, “compatible” mixtures of water and medium chain head group surfactants or alkylene cross-linked surfactants are transparent or translucent and poured at temperatures in the range of about 15 ° C. to 25 ° C. Flows easily when pumping up. This product form facilitates handling, shipping, and formulation from a commercial point of view.

  Suitable solvents include, for example, isopropanol, ethanol, 1-butanol, ethylene glycol, n-butanol ether, Dowanol® series solvents, propylene glycol, butylene glycol, propylene carbonate, ethylene carbonate, solketal, and the like. Similar things are included. Preferably, the composition is less than 25% by weight (based on the total amount of medium chain head group surfactant or alkylene cross-linking surfactant, solvent, hydrotrope, and any co-surfactant), more preferably It should contain less than 15% by weight, optimally less than 10% by weight of solvent.

  Hydrotropes can improve the water solubility of organic compounds that are usually only slightly soluble in water. Hydrotropes suitable for formulating cold water detergents are preferably short chain surfactants that help solubilize other surfactants. Hydrotropes suitable for use herein include, for example, aryl sulfonates (eg, cumene sulfonate, xylene sulfonate), short chain alkyl carboxylates, sulfosuccinates, urea, short chain alkyls. Sulfates, short chain alkyl ether sulfates, and the like, and combinations thereof are included. When hydrotrope is present, the composition is less than 25% by weight (based on the total amount of medium chain head group surfactant or alkylene cross-linking surfactant, solvent, hydrotrope, and any cosurfactant). Preferably it contains a hydrotrope, more preferably it contains less than 10 wt% hydrotrope.

Suitable co-surfactants include, for example, N, N-diethanol oleamide, N, N-diethanol C ₈ -C ₁₈ saturated or unsaturated aliphatic amides, ethoxylated fatty alcohols, alkyl polyglucosides, alkyls Amine oxide, N, N-dialkyl aliphatic amide, oxide of N, N-dialkylaminopropyl aliphatic amide, N, N-dialkylaminopropyl aliphatic amide, alkylbetaine, linear C ₁₂ -C ₁₈ sulfate or Examples include sulfonates, alkyl sulfobetaines, alkylene oxide block copolymers of aliphatic alcohols, alkylene oxide block copolymers, and the like. Preferably, the composition comprises less than 25% by weight cosurfactant (based on the total amount of medium chain head group surfactant or alkylene cross-linking surfactant, cosurfactant, and optional solvent); More preferably, it comprises less than 15% by weight cosurfactant and optimally less than 10% by weight cosurfactant.

  In another preferred embodiment, the cold water washing method is performed using a specific laundry detergent formulation comprising a lipase and a medium chain head group surfactant or an alkylene crosslinked surfactant.

One such laundry detergent composition comprises 5 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or alkylene cross-linked surfactant and has a pH in the range of 7-10. . This detergent further comprises:
0% to 50% by weight of at least one nonionic surfactant;
0% to 25% by weight of at least one alcohol ether sulfate; and
Cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, and these A sufficient amount of at least two enzymes selected from the group consisting of:

Another such laundry detergent composition comprises 5-95% by weight of a laundry detergent comprising lipase and a medium chain head group surfactant or an alkylene cross-linked surfactant and has a pH in the range of 7-10. . This detergent further comprises:
0% to 50% by weight of at least one nonionic surfactant;
0% to 25% by weight of at least one alcohol ether sulfate; and
Cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, and these A sufficient amount of one enzyme selected from the group consisting of:

Another such laundry detergent composition comprises 5 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or an alkylene cross-linked surfactant and has a pH in the range of 7-12. Except for lipase, it is substantially free of enzymes. This detergent further comprises:
0% to 50% by weight of at least one nonionic surfactant; and
0% to 25% by weight of at least one alcohol ether sulfate.

Another such laundry detergent composition comprises 5 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or an alkylene crosslinked surfactant and has a pH in the range of 7-12. This detergent further comprises:
4% to 50% by weight of at least one C ₁₆ α-methyl ester sulfate; and
0% to 25% by weight of cocamide diethanolamine.

Another such laundry detergent composition comprises 5 to 95% by weight of a detergent comprising a lipase and a medium chain head group surfactant or an alkylene crosslinked surfactant and has a pH greater than 10. This detergent further comprises:
0% to 50% by weight of at least one nonionic surfactant;
0% to 25% by weight of at least one alcohol ether sulfate; and
0.1 wt% to about 5 wt% metasilicate.

Another such laundry detergent composition comprises 5 to 95% by weight of a detergent comprising a lipase and a medium chain head group surfactant or an alkylene crosslinked surfactant and has a pH greater than 10. This detergent further comprises:
0% to 50% by weight of at least one nonionic surfactant;
0% to 25% by weight of at least one alcohol ether sulfate; and
0.1% to 20% by weight of sodium carbonate.

Another such laundry detergent composition comprises 2 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or an alkylene cross-linked surfactant. This detergent further comprises:
2% to 40% by weight of at least one nonionic surfactant;
0% to 32% by weight of at least one alcohol ether sulfate;
0% to 25% by weight of at least one C ₁₆ α-methyl ester sulfate;
0% to 6% by weight of lauryldimethylamine oxide;
0% to 6% by weight _C 12 _EO 3;
0% to 10% by weight of coconut fatty acid;
0% to 3% by weight of sodium borate pentahydrate;
0% to 6% by weight of propylene glycol;
0% to 10% by weight of sodium citrate;
0% to 6% by weight of triethanolamine;
0% to 6% by weight of monoethanolamine;
0% to 1% by weight of at least one fluorescent whitening agent;
0% to 1.5% by weight of at least one anti-redeposition agent;
0% to 2% by weight of at least one thickener;
0% to 2% by weight of at least one diluent;
0% to 2% by weight of at least one protease;
0% to 2% by weight of at least one amylase; and
0% to 2% by weight of at least one cellulase.

Yet another such laundry detergent composition comprises 2 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or an alkylene cross-linked surfactant. This detergent further comprises:
2% to 40% by weight of at least one nonionic surfactant;
0% to 32% by weight of at least one alcohol ether sulfate;
0% to 6% by weight of lauryldimethylamine oxide;
0% to 6% by weight _C 12 _EO 3;
0% to 10% by weight of coconut fatty acid;
0% to 10% by weight of sodium metasilicate;
0 wt% to 10 wt% sodium carbonate;
0% to 1% by weight of at least one fluorescent whitening agent;
0% to 1.5% by weight of at least one anti-redeposition agent;
0% to 2% by weight of at least one thickener; and
0% to 2% by weight of at least one diluent.

Another “environmentally friendly” laundry detergent composition comprises 2 to 95% by weight of a detergent comprising lipase and a medium chain head group surfactant or an alkylene cross-linked surfactant. This detergent further comprises:
0 wt% to 30 wt% of at least one _{C 16} methyl ester sulfates;
0 wt% to 30 wt% of at least one _{C 12} methyl ester sulfates;
0-30% by weight sodium lauryl sulfate;
0-30% by weight sodium stearoyl lactylate;
0-30% by weight sodium lauroyl lactate;
0% to 60% by weight of alkyl polyglucoside;
0% to 60% by weight of polyglycerol monoalkylate;
0% to 30% by weight of lauryl lactyl lactate;
0% to 30% by weight of saponin;
0-30% by weight of rhamnolipid;
0% to 30% by weight of sphingolipids;
0% to 30% by weight of glycolipids;
0% to 30% by weight of at least one abietic acid derivative; and
0% to 30% by weight of at least one polypeptide.

  In one aspect, lipases and medium chain head group surfactants or alkylene cross-linked surfactants are used in pre-spotter laundry compositions. In this application, the grease stain or oil stain on the garment or fabric is brought into direct contact with the pre-bleed prior to hand washing or machine washing. The fabric or garment is preferably treated for 5 to 30 minutes. The amount of active medium chain head group surfactant or alkylene cross-linking surfactant in the pre-bleaching composition is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, more preferably 5 to 20%. It is optimal to be weight percent. The fabric to be treated is preferably at a temperature in the range of 5-30 ° C, more preferably at a temperature in the range of 10-20 ° C, optimally in the range of 12-18 ° C. At temperature, usually machine washed.

  In another aspect, lipases and medium chain head group surfactants or alkylene cross-linked surfactants are used in pre-soaked compositions for hand or machine cleaning.

  When used for hand washing, the pre-soaked composition is combined with cold water in a washing tub or other container. The amount of active medium chain head group surfactant or alkylene cross-linking surfactant in the pre-soaked composition is preferably 0.5 to 100% by weight, more preferably 1 to 80% by weight. It is optimal that it is ˜50% by weight. The garment or fabric is preferably immersed in a pre-soak in a bag, soaked for 15-30 minutes and washed as usual.

  When used for machine cleaning, the pre-soaked composition has a temperature in the range of 5 ° C. to 30 ° C., more preferably a temperature in the range of 10 ° C. to 20 ° C., optimally 12 ° C. Preferably added to a machine containing water at a temperature in the range of -18 ° C. The amount of active medium chain head group surfactant or alkylene crosslinking surfactant in the pre-soaked composition is preferably 0.5-100 wt%, more preferably 1-80 wt%, 5 to 50% by weight is optimal. The garment / fabric is added to the machine, soaked for 5 to 10 minutes (usually with a pre-soak cycle selected in the machine) and then washed as usual.

  In another aspect, lipases and medium chain head group surfactants or alkylene cross-linked surfactants are used as additives for laundry products or laundry formulations. In such applications, the surfactant helps to improve or promote the oil removal performance or oil reduction performance of the laundry article or laundry formulation. The amount of medium chain head group surfactant or alkylene cross-linked surfactant active used is in the range of 1 to 10 wt%, more preferably 2 to 8 wt%, and 3 to 5 wt%. And is optimal. Preferably, the laundry article or laundry formulation and the medium chain head group surfactant or alkylene cross-linked surfactant are mixed until a uniform composition is obtained.

  In yet another aspect, lipases and medium chain head group surfactants or alkylene cross-linked surfactants are used as surfactant additives. In such applications, the resulting modified surfactant improves fat removal or fat reduction properties. Preferably, the amount of medium chain head group surfactant or alkylene cross-linked surfactant active used is in the range of 1-10 wt%, more preferably 2-8 wt%, more preferably 3-5 wt% % Is optimal. The resulting modified surfactant will help to achieve improved oil reduction / removal performance in commercial products. Such products may be used at temperatures in the range of 5 ° C to 30 ° C, and are preferably used at temperatures in the range of 10 ° C to 20 ° C, and in the range of 12 ° C to 18 ° C. More preferably it is used at temperature.

(General considerations for strong liquid (HDL) laundry detergents)
Desirable surfactant properties for HDL include being in liquid form at room temperature, ability to be formulated in cold mix applications, and functioning as well as or better than existing surfactants Includes abilities.

  Desirable properties for HDL include dirt, oils, or fines after milking, suspending or penetrating fats or oil stains, for example, to clean surfaces, and penetrating or dispersing particles. The ability to inhibit re-deposition of particulate matter on a newly cleaned surface is included.

  In order to use HDL in high efficiency washers (all high efficiency (HE) washers need to be understood to include all of the front insert washers as well), It is also desirable to have the ability to control. Small foam is desirable to achieve optimal cleaning and to avoid excessive foaming. Other desirable properties include the ability to purify the formulation and the ability to improve long-term storage stability at both harsh outdoor and normal room temperatures.

  One of ordinary skill in the art will understand that the medium chain head group surfactants or alkylene cross-linked surfactants of the present disclosure are usually not merely “compatible” substitutes for existing detergent formulations. . In order to achieve desirable results in terms of appearance, handling, solubility characteristics and other physical properties and performance attributes, typically other surfactants, hydrotropes, alkali modifiers, and / or formulations Some amount of recombination is required to adjust the nature and amount of the other ingredients. For example, the formulation uses higher amounts of ethoxylated nonionic surfactants in place of surfactants with a small amount of EO units in combination with medium chain head group surfactants or alkylene cross-linked surfactants. You may need to be adjusted by doing. The type of recombination is considered to be within normal skill and is left to the discretion of those skilled in the art.

(Detergent composition)
A wide range of detergent compositions can be made with medium chain head group surfactants or alkylene cross-linked surfactants and with or without other components as specified below. 1 to 99%, more preferably 1% to 60%, even more preferably 1% to 30%, with 99% to 1% water, and optionally other ingredients as disclosed herein Formulations containing a medium chain head group surfactant or an alkylene crosslinked surfactant are contemplated.

(Surfactant)
The detergent composition can include a co-surfactant. The co-surfactant may be anionic, cationic, nonionic, amphoteric, zwitterionic, or a combination thereof.

(Anionic surfactant)
Formulations useful in the method of the present invention can include an anionic surfactant in addition to the medium chain head group surfactant or alkylene cross-linked surfactant. An “anionic surfactant” as used herein generally has an average molecular weight of less than about 10,000 and is present in an aqueous solvent at normal wash pH, which can be 6-11. Defined as an amphiphilic molecule containing one or more functional groups exhibiting anionic charge. The anionic surfactant may be any anionic surfactant that is substantially water soluble. “Water-soluble” surfactants are defined herein to include surfactants that can be dissolved or dispersed in distilled water at about 0.01% by weight at 25 ° C., unless otherwise specified. At least one of the anionic surfactants used may be an alkali metal salt or alkaline earth metal salt of a natural or synthetic fatty acid containing from about 4 to about 30 carbon atoms. Mixtures of carboxylates with one or more other anionic surfactants may be used. Another important class of anionic compounds is the water-soluble salts of organic sulfur reaction products, especially alkali metal salts. The organic sulfur reaction product has in its molecular structure an alkyl radical containing about 6 to about 24 carbon atoms and a radical selected from the group consisting of sulfonate radicals and sulfate radicals. ing.

  Specific types of anionic surfactants are revealed in the following paragraphs. In some embodiments, alkyl ether sulfates are preferred. In other embodiments, linear alkyl benzene sulfonates are preferred.

  The carboxylate is represented by the following formula:

ここで、Ｒ^１は４〜３０炭素原子の第１又は第２アルキル基であり、Ｍは可溶化カチオンである。Ｒ^１によって表されるアルキル基は、複数の鎖長の混合物として示され、飽和であってもよく、不飽和であってもよいが、Ｒ^１基の少なくとも３分の２が、８〜１８の炭素原子の鎖長を有していることが好ましい。好適なアルキル基源の非限定的な例には、ココナッツオイル、獣脂、トールオイル、及びパーム核油から誘導される脂肪酸が含まれる。しかしながら、臭気を最小にするために、第１級飽和カルボン酸を用いることが望ましいことが多い。このような材料は、当業者に公知であり、ユニケマ社（デラウェア州ウィルミントン）及びツイン・リバーズ・テクノロジー社（マサチューセッツ州クインシー）のような多くの商業的供給源から入手できる。可溶化カチオン、即ちＭは、水溶性を前記生成物に授与する任意のカチオンであってもよいが、一般的には、一価のそのような部分が好ましい。本技術での使用のために許容可能な可溶化カチオンには、ナトリウム及びカリウム（これらが特に好ましい）のようなアルカリ金属、及びトリエタノールアミン、アンモニウム及びモルホリニウムのようなアミンが含まれる。使用される場合には、脂肪酸の大部分は、中性塩の形態で配合物中に組み込まれる必要があるが、該配合物中において、少量の遊離脂肪酸をそのままの状態にしておくことが好ましいことが多い。その理由は、少量の遊離脂肪酸は、生成物の粘度の維持を補助できるからである。

Here, R ¹ is a primary or secondary alkyl group of 4 to 30 carbon atoms, and M is a solubilizing cation. The alkyl group represented by R ¹ is shown as a mixture of multiple chain lengths and may be saturated or unsaturated, but at least two thirds of the R ¹ groups are 8-18. It is preferable to have a chain length of carbon atoms. Non-limiting examples of suitable alkyl group sources include fatty acids derived from coconut oil, tallow, tall oil, and palm kernel oil. However, it is often desirable to use primary saturated carboxylic acids to minimize odor. Such materials are known to those skilled in the art and are available from a number of commercial sources such as Unikema (Wilmington, Del.) And Twin Rivers Technology (Quincy, Mass.). The solubilizing cation, ie M, may be any cation that confers water solubility to the product, but in general, a monovalent such moiety is preferred. Acceptable solubilizing cations for use in the present technology include alkali metals such as sodium and potassium (which are particularly preferred) and amines such as triethanolamine, ammonium and morpholinium. When used, the majority of the fatty acids need to be incorporated into the formulation in the form of neutral salts, but it is preferable to leave a small amount of free fatty acids intact in the formulation. There are many cases. The reason is that small amounts of free fatty acids can help maintain the viscosity of the product.

  The primary alkyl sulfate is represented by the following formula.

ここで、Ｒ^２は、８〜１８の炭素原子の第１級アルキル基であり、分岐又は直鎖、飽和又は不飽和であってもよい。Ｍは、Ｈ若しくはカチオン、例えば、アルカリ金属カチオン（例えば、ナトリウム、カリウム、リチウム）、又はアンモニウム若しくは置換アンモニウム（例えば、メチル−、ジメチル−、及びトリメチルアンモニウムカチオン、並びにテトラメチルアンモニウムのような四級アンモニウムカチオン、並びにジメチルピペリジンカチオン、並びにエチルアミン、ジエチルアミン、トリエチルアミン、及びこれらの混合物、並びにこれに類するものから誘導される四級アンモニウム）である。アルキル基Ｒ^２は、複数の鎖長の混合物を有していてもよい。Ｒ^２基の少なくとも３分の２が、８〜１４の炭素原子の鎖長を有している。例えば、Ｒ^２がココナッツアルキルの場合がこの例になる。可溶化カチオンは、一般に１価であり、水溶性を授与する種々のカチオンであってもよい。アルカリ金属、特に、ナトリウムが想定される。他の可能なものは、アンモニウムイオン及びトリアルカノールアンモニウム又はトリアルキルアンモニウムのような置換アンモニウムイオンである。

Here, R ² is a primary alkyl group of 8 to 18 carbon atoms, and may be branched or linear, saturated or unsaturated. M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium), or an ammonium or substituted ammonium (eg, methyl-, dimethyl-, and trimethylammonium cations, and a quaternary such as tetramethylammonium. Ammonium cations, and dimethylpiperidine cations, and quaternary ammoniums derived from ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Alkyl group R ² may have a mixture of chain lengths. At least two thirds of the R ² groups have a chain length of 8 to 14 carbon atoms. For example, this is the case when R ² is coconut alkyl. The solubilizing cation is generally monovalent and may be various cations that confer water solubility. Alkali metals, particularly sodium, are envisioned. Other possible are ammonium ions and substituted ammonium ions such as trialkanol ammonium or trialkyl ammonium.

  The alkyl ether sulfate is represented by the following formula.

ここで、Ｒ^３は、８〜１８の炭素原子の第１級アルキル基であり、分岐又は直鎖、飽和又は不飽和であり、ｎは、平均値が１〜６の範囲内であり、Ｍは、可溶化カチオンである。アルキル基Ｒ^３は、複数の鎖長の混合物を有していてもよい。Ｒ^３アルキル基の少なくとも３分の２が、８〜１８の炭素原子の鎖長を有していることが好ましい。例えば、Ｒ^３がココナッツアルキルの場合がこの例である。ｎは２〜５の平均値であると好ましい。エーテル硫酸塩が、本技術の配合物の特定の例において、粘度の増加を提供することが分かる。これにより、エーテル硫酸塩は好ましい成分であると考えられる。

Where R ³ is a primary alkyl group of 8 to 18 carbon atoms, branched or straight chain, saturated or unsaturated, n is in the range of 1 to 6 on average, M Is a solubilized cation. The alkyl group R ³ may have a mixture of a plurality of chain lengths. It is preferred that at least two thirds of the R ³ alkyl group has a chain length of 8 to 18 carbon atoms. An example of this is when R ³ is coconut alkyl. n is preferably an average value of 2 to 5. It can be seen that ether sulfate provides increased viscosity in certain examples of formulations of the present technology. Thus, ether sulfate is considered a preferred component.

Other preferred anionic surfactants that can be used are alkyl ester sulfate surfactants containing linear esters of C _{8 to} C ₂₀ carboxylic acids (ie fatty acids). The linear ester is sulfonated with gaseous SO ₃ (see, for example, J. Am. Oil Chem. Soc. 52 (1975) 323). Suitable starting materials will include fatty substances such as those derived from tallow, palm oil, and the like.

  Particularly preferred alkyl ester surfactants for laundry applications include alkyl ester sulfate surfactants of the following structural formula:

ここで、Ｒ^３は、好ましくは、Ｃ_６〜Ｃ_２０ヒドロカルビルであり、アルキル又はそれらの組み合わせであり、Ｒ^４は、Ｃ_１〜Ｃ_６ヒドロカルビルであり、好ましくは、アルキル又はそれらの組み合わせであり、Ｍは、アルキルエステル硫酸塩と水溶性塩を形成するカチオンである。好適な塩形成カチオンには、ナトリウム、カリウム、及びリチウムなどの金属、並びに、モノエタノールアミン、ジエタノールアミン、及びトリエタノールアミンのような置換又は非置換のアンモニウムカチオンが含まれる。Ｒ^３基は、複数の鎖長の混合物を有していてもよい。これらの基の少なくとも３分の２が、６〜１２個の炭素原子を有している。例えば、Ｒ^３ＣＨ（−）ＣＯ_２（−）がココナッツ源から誘導される場合がこの例となる。好ましくは、Ｒ^３はＣ_１０〜Ｃ_１６アルキルであり、Ｒ^４はメチル、エチル、又はイソプロピルである。特に好ましいのは、Ｒ^３がＣ_１０〜Ｃ_１６アルキルであるメチルエステルスルホン酸塩である。

Here, R ³ is preferably C ₆ -C ₂₀ hydrocarbyl and is alkyl or a combination thereof, and R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl or a combination thereof. , M is a cation that forms a water-soluble salt with the alkyl ester sulfate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, and triethanolamine. The R ³ group may have a mixture of a plurality of chain lengths. At least two thirds of these groups have 6 to 12 carbon atoms. An example of this is when R ³ CH (−) CO ₂ (−) is derived from a coconut source. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates where R ³ is C ₁₀ -C ₁₆ alkyl.

  The alkylbenzene sulfate is represented by the following formula.

ここで、Ｒ^６は、８〜１８の炭素原子のアルキル基であり、Ａｒは、ベンゼン環（−Ｃ_６Ｈ_４−）であり、Ｍは可溶化カチオンである。Ｒ^６基は、複数の鎖長の混合物であってもよい。典型的には、異性体の混合物が使用される。「高級２−フェニル」及び「低級２−フェニル」のような多数の異なる等級が、必要とする配合物に応じた使用のために市販されている。ステパン社、アクゾ社、パイロット社、及びロディア社を含む、これらの材料のための多数の商品製造業者が存在する。典型的には、配合物は、アルキルベンゼンのスルホン化によって得られる。アルキルベンゼンは、オレフィンとのベンゼンのＨＦ触媒アルキル化又はベンゼンをクロロパラフィンとアルキル化するＡｌＣｌ_３触媒プロセスによって得ることができる。配合物は、例えば、ペトレサ社（イリノイ州シカゴ）、及びサソール社（テキサス州オースティン）によって販売されている。通常、１１〜１４の炭素原子の直鎖のものが好ましい。

Here, R ⁶ is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (—C ₆ H ₄ —), and M is a solubilizing cation. The R ⁶ group may be a mixture of a plurality of chain lengths. Typically, a mixture of isomers is used. A number of different grades such as “higher 2-phenyl” and “lower 2-phenyl” are commercially available for use depending on the formulation required. There are a number of commodity manufacturers for these materials, including Stepan, Akzo, Pilot and Rhodia. Typically, formulations are obtained by sulfonation of alkylbenzenes. Alkylbenzenes can be obtained by HF catalyzed alkylation of benzene with olefins or AlCl ₃ catalyzed processes in which benzene is alkylated with chloroparaffins. Formulations are sold, for example, by Petresa (Chicago, IL) and Sasol (Austin, TX). Usually a straight chain of 11 to 14 carbon atoms is preferred.

  Paraffin sulfonates having about 8 to about 22, preferably about 12 to about 16 carbon atoms in the alkyl moiety are envisioned for use herein. Paraffin sulfonic acids are usually obtained by sulfoxidation of linear paraffins derivatized by petrochemical processing. These surfactants are commercially available, for example, as Hostapur SAS from Clariant (Charlotte, NC).

  Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, are also envisioned for use in the present compositions. Olefin sulfonates are 0-1 ethylene double bonds, 1-2 sulfonate sites (one is a terminal group, the other is not a terminal group), and 0-1 second. Characterized as having a hydroxyl site. U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates. That teaching is incorporated herein by reference. Specific surfactant species derived from this patent include the following:

  In the above formula, x is an integer from about 4 to about 18, preferably from about 4 to about 12, M represents any cation, which includes alkali metals (eg, sodium and potassium) and ammonium and Water-soluble salts such as substituted ammonium compounds (eg, trialkylammonium and trialkylammonium compounds) are formed. Specific examples of substituted ammonium compounds are triethylammonium, trimethylammonium, and triethanolammonium. Others will be apparent to those skilled in the art. Such a material is sold, for example, as Bio-Target® AS-40 (product of Stepan).

  The sulfosuccinic acid ester is represented by the following formula:

該式の化合物も、本明細書において、アニオン性界面活性剤として有用である。Ｒ^７及びＲ^８は、２〜１６の炭素の鎖長を有するアルキル基であり、直鎖又は分岐され、飽和又は不飽和であってもよい。好ましいスルホコハク酸は、ビス（２−エチルヘキシル）スルホコハク酸ナトリウムであり、これは、サイテック・インダストリー社（ニュージャージー州ウエスト・パターソン）から商品名Ａｅｒｏｓｏｌ ＯＴの下に市販されている。

The compounds of the formula are also useful herein as anionic surfactants. R ⁷ and R ⁸ are alkyl groups having a chain length of 2 to 16 carbons and may be linear or branched and saturated or unsaturated. A preferred sulfosuccinic acid is sodium bis (2-ethylhexyl) sulfosuccinate, which is commercially available from Cytec Industries (West Patterson, NJ) under the trade name Aerosol OT.

  Organophosphorus anionic surfactants include organophosphates such as mono- or diester phosphate complexes of terminal hydroxyl alkoxide condensates, or salts thereof. Suitable organophosphate esters include phosphate esters of polyalkylated alkylarylphenols, phosphate esters of ethoxylated linear alcohols, and phosphate esters of ethoxylated phenols. Also included are nonionic alkoxylates having an alkylene carboxylate sodium moiety bonded to the terminal hydroxyl group of the nonionic surfactant via an ether linkage. The counter ions of all the salts may be counter ions of alkali metal, alkaline earth metal, ammonium, alkanol ammonium, and alkyl ammonium species.

Other anionic surfactants useful for cleaning purposes can also be included in the cleaning composition. These include soap salts (eg, sodium salts, potassium salts, ammonium salts, and substituted ammonium salts such as mono-, di-, and triethanolamine salts), C ₈ -C ₂₂ primary or secondary alkane sulfones. Sulfonation prepared by sulfonation of pyrolysis products of acid salts, C _{8 to} C ₂₄ olefin sulfonates, eg alkaline earth metal citrates as described in GB 1082179 polycarboxylic acids, C ₈ -C ₂₄ (comprising ethylene oxide up to 10 mol) alkyl polyglycol ether sulfates, alkyl glycerol sulfates, fatty acyl glycerol sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates , Paraffin sulfate, alkyl phosphate, reed Isethionate such as isethionic acid, N- acyl taurates, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially, C ₁₂ -C ₁₈ monoesters of saturated and unsaturated) and sulfosuccinate diester salts (particularly, C ₆ -C ₁₂ diesters of saturated and unsaturated), alkyl polysaccharides sulfates such as sulfates of alkyl polyglycosides (hereinafter nonionic compounds that are not sulfated described in) , and formula _{RO (CH 2 CH 2 O)} k CH 2 COO - M + ( wherein, R is _C 8 _{-C 22} alkyl, k is an integer of 0, M is a water-soluble salt-forming cation Alkyl polyethoxycarboxylate salts such as Also suitable are resin acids and hydrogenated resin acids such as resin acids and hydrogenated resin acids that are present in or derived from rosin, hydrogenated rosin, and tall oil. Further examples are disclosed in "Surface Active Agent and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Such various surfactants are generally also disclosed in US Pat. Nos. 3,929,678 and 6,949,498. These teachings are incorporated herein by reference.

  Other anionic surfactants envisioned include isethionate, sulfated triglycerides, alcohol sulfate, lignin sulfate, naphthalene sulfate, and alkyl naphthalene sulfate, and the like.

  Specific anionic surfactants envisioned for use in the present composition include alcohol ether sulfate (AES), linear alkylbenzene sulfate (LAS), alcohol sulfate (AS), alpha methyl ester Sulfate (MES) or a combination of two or more thereof is included. The amount of anionic surfactant envisaged may be, for example, 1% to 70% of the composition, more preferably 1% to 60%, and even more preferably 1% to 40%. For a more general description of surfactants, see US Pat. No. 5,929,022. This teaching is incorporated herein by reference.

(Nonionic and amphoteric surfactants)
Examples of suitable nonionic surfactants include alkyl polyglycoside (APG) alcohol ethoxylates, nonylphenol ethoxylates, methyl ester ethoxylates (MEE), and others. Nonionic surfactants may be used at 1-90% of the detergent composition, more preferably 1-40%, optimally 1-32%. Other suitable nonionic surfactants are disclosed in US Pat. No. 5,929,022. From that specification, much of the following discussion arises.

  One class of nonionic surfactants useful herein is an average hydrophilic parent in the range of 8-17, preferably in the range of 9.5-14, more preferably in the range of 12-14. It is a condensate of ethylene oxide and hydrophobic moieties to provide a surfactant with an oil balance (HLB). Hydrophobic (lipophilic) sites are aliphatic or aromatic and the length of the polyoxyethylene group condensed with any particular hydrophobic group is the desired degree between the hydrophilic and hydrophobic elements Can be easily adjusted to obtain a water-soluble compound having the following balance:

  In the case of “low HLB” non-ionic, low HLB may be defined as HLB less than 8, preferably less than 6. A “low level” of co-surfactant may be defined as less than 6% HDL, preferably less than 4% HDL.

Particularly preferred nonionic surfactants of this type are C _{9 to} C ₁₅ primary alcohol ethoxylates containing 3 to 12 moles of ethylene oxide per mole of alcohol, preferably 5 to 8 moles per mole of alcohol. C ₁₂ -C ₁₅ primary alcohol containing ethylene oxide. One suitable example of such a surfactant is a polyalkoxylated aliphatic base sold, for example, as Makon® NF-12 by the company Stepan Company.

  Another example of a nonionic surfactant comprises an alkyl polyglycoside compound of the general formula:

ここで、Ｚはグルコースから誘導される部位であり、Ｒは、１２〜１８の炭素原子を含む飽和の疎水性アルキル基であり、ｔは、０〜１０であり、ｎは２又は３である。ｘは、１．３〜４の平均数を有する。前記化合物は、１０％未満の未反応脂肪族アルコール及び５０％未満の短鎖アルキルポリグリコシドを含む。この種の化合物及び洗剤組成物での使用については、欧州特許第００７００７７号明細書、欧州特許第００７５９９６号明細書、及び欧州特許第００９４１１８号明細書中に開示されている。

Here, Z is a site derived from glucose, R is a saturated hydrophobic alkyl group containing 12 to 18 carbon atoms, t is 0 to 10, and n is 2 or 3. . x has an average number of 1.3-4. The compound comprises less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglycoside. Such compounds and their use in detergent compositions are disclosed in EP 0070077, EP 0075996, and EP 0094118.

  Also suitable as nonionic surfactants are polyhydroxyl fatty acid amide surfactants of the following formula:

ここで、Ｒ^１はＨ、又はＲ^１はＣ_１−４ヒドロカルビル、２−ヒドロキシエチル、２−ヒドロキシプロピル、又はこれらの混合物であり、Ｒ^２は、Ｃ_５〜Ｃ_３１ヒドロカルビルであり、Ｚは、直鎖ヒドロキシカルビル鎖を有し、該鎖に直に接続されている少なくとも３つのヒドロキシル基を有するポリヒドロキシカルビル、またはそのアルコキシル化された誘導体である。該ポリヒドロキシカルビルは、直鎖ヒドロカルビル鎖であって、少なくとも３個のヒドロキシル基が該鎖に接続されている直鎖ヒドロカルビル、又はそのアルコキシル化された誘導体を有する。好ましくは、Ｒ^１はメチルであり、Ｒ^２は、ココナッツアルキルのような直鎖Ｃ_{１１−１５}アルキル又はアルケニル鎖又はこれらの混合物であり、Ｚは、還元的アミノ化反応において、グルコース、フルクトース、マルトース、ラクトースのような還元糖から誘導される。

Where R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is A polyhydroxycarbyl having a straight hydroxycarbyl chain and having at least three hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof. The polyhydroxycarbyl has a linear hydrocarbyl chain having at least three hydroxyl groups connected to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or alkenyl chain such as coconut alkyl or a mixture thereof, and Z is glucose, fructose, in a reductive amination reaction Derived from reducing sugars such as maltose and lactose.

  Amphoteric synthetic detergents are widely disclosed as aliphatic derivatives or derivatives of aliphatic secondary and tertiary amines. In these, the aliphatic radical may be linear or branched, one of the aliphatic substituents containing from about 8 to about 18 carbon atoms, at least one of which is an anionic water solubilizing group (eg, , Carboxy, sulfo, sulfato, phosphato, or phosphono (see US Pat. No. 3,664,961, the teachings of which are incorporated herein by reference). Suitable amphoteric surfactants include aliphatic amine oxides and aliphatic amidopropyl amine oxides. Particular suitable examples are cocoamidopropyl betaine (CAPB) and coco betaine (CB). Amphoteric surfactants may be used in an amount of 1% to 50%, more preferably 1% to 10%, even more preferably 1% to 5% by weight of the formulation.

  Amine oxide surfactants are highly preferred. The compositions herein may comprise an amine oxide according to the general formula:

In general, the previous formula provides one long chain site, R ¹ (EO) _x (PO) _y (BO) _z, and two short chain sites, —CH ₂ R ′. Can be understood. R ′ is preferably selected from hydrogen, methyl, and —CH ₂ OH. In general, R ¹ is a primary or branched hydrocarbyl moiety that may be saturated or unsaturated, and preferably R ¹ is a primary alkyl moiety. When x + y + z = 0, R ¹ is a hydrocarbyl moiety having a chain length of about 8 to about 18. When x + y + z is not 0, R ¹ is slightly longer and has a chain length in the range of C _{12 to} C ₂₄ . Here, when x + y + z = 0, R ¹ is C ₈ -C ₁₈ , R ′ is H, q = 0-2, preferably 2, the general formula also contains an amine oxide. These amine oxides are represented by C _12-14 alkyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, octadecyl amine oxide, and hydrates thereof, in particular, US Pat. Nos. 5,075,501 and 5,071,594. Shown as the dihydrate as disclosed in. These teachings are incorporated herein by reference.

If x + y + z is not 0, amine oxides are also suitable. Specifically, when x + y + z is about 1 to about 10, R ¹ is a primary alkyl group containing about 8 to about 24 carbons, preferably about 12 to about 16 carbon atoms. In these embodiments, y + z is preferably 0 and x is preferably from about 1 to about 6, and more preferably from about 2 to about 4. EO represents ethyleneoxy, PO represents propyleneoxy, and BO represents butyleneoxy. Such amine oxides may be prepared by conventional synthetic methods, for example by oxidizing the ethoxylated amine with hydrogen peroxide after reaction of the alkyl ethoxysulfate with dimethylamine.

  Preferred amine oxides are solid at ambient temperature. More preferably, the amine oxide has a melting point in the range of 30 ° C to 90 ° C. Amine oxides suitable for use are made commercially by Stepan, Akzo Chemie, Ethyl Corporation, Protector and Gambling, and other companies. See McCutcheon's compilation and Kirt-Othmer review paper for alternative amine oxide manufacturers. Preferred commercially available amine oxides are Ammonyx® LO and Ammonyx® MO surfactants (Stepan).

  Preferred detergents include, for example, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris (ethyleneoxy) dimethylamine oxide, and tetradecyldimethylamine oxide dihydrate. .

In certain embodiments where R ′ is H, there is some flexibility in having R ′ slightly greater than H. Specifically, in the case of hexadecyl bis (2-hydroxyethyl) amine oxide, tallow bis (2-hydroxyethyl) amine oxide, stearyl bis (2-hydroxyethyl) amine oxide, and olebis (2-hydroxyethyl) amine oxide. As such, R ′ may be CH ₂ OH.

(Zwitterionic surfactant)
Zwitterionic synthetic detergents can be widely disclosed as derivatives of aliphatic quaternary ammonium and phosphonium, or tertiary sulfonium compounds. In the compound, the cation atom may be part of a heterocyclic ring, in which the aliphatic radical may be linear or branched, and one of the aliphatic substituents is about 3 to 3 Containing at least about 18 carbon atoms and at least one aliphatic substituent is an anionic water solubilizing group such as carboxyl, sulfo, sulfato, phosphato, or phosphono (see US Pat. No. 3,664,961). Are incorporated herein by reference). Zwitterionic surfactants are used at 1 wt% to 50 wt%, more preferably 1 wt% to 10 wt%, even more preferably 1 wt% to 5 wt%, based on the formulation. May be.

  Any mixture of two or more individual contemplated surfactants, whether homogeneous or heterogeneous, is contemplated herein.

(Laundry detergent composition)
The formulation and use of surfactants according to the present invention will be described in more detail for laundry detergent compositions.

  The four desirable properties of laundry detergent compositions, particularly liquid compositions (the disclosure is not limited to liquid compositions, or compositions having any or all of these properties) are (1) concentrated The formulation is beneficial in saving retailer shelf space, (2) “Environmentally friendly” or environmentally friendly compositions are beneficial, (3) Washing garments over conventional machines Useful for compositions that function in modern high efficiency washers that use less energy and water to do and (4) cold water, i.e. less than 30 ° C, preferably better at 5-30 ° C A composition to be washed.

  To save a substantial amount of retailer shelf space, as a conventional laundry detergent, 2 or even 3, 4, 5, 6 or even multiples (eg, 8 times) per unit volume or unit quantity Concentrated formulations with the following efficacy are envisaged. When less water is used, the composition of the detergent composition becomes complicated. This is because the formulation needs to be more soluble and otherwise needs to work well when diluted with a relatively small amount of water.

  For “environmentally friendly” formulations, the surfactant may ultimately be biodegradable and non-toxic. In order to satisfy consumer perception and reduce the use of petrochemicals, “environmentally friendly” formulations also advantageously use renewable hydrocarbons such as vegetable or animal oils in the production of surfactants. It may be limited to.

  High efficiency (HE) washers present several challenges to the cleaning formulation. As of January 2011, all washers sold in the United States need to be at least somewhat efficient, and this requirement will only become more limited next year. Front-insertion machines (all of which are high efficiency machines) exhibit the highest efficiency and are increasingly used.

  Because the use of very small amounts of water requires that a small amount of foam be generated during the wash cycle, strong liquid detergent formulations are affected by high efficiency machines. As water usage continues to decline in future high efficiency machines, detergents may be required to be moved in a direction that does not produce foam. In addition, high efficiency HDL needs to be quickly and neatly dispersed at low cleaning temperatures.

  In order to function in modern high efficiency washers, these washers use a relatively small amount of water and lower washes than conventional machines so that the detergent composition is in a relatively concentrated form in cold water. It is required to function in. Such foaming of high efficiency formulations may be reduced or even removed in a small amount of water environment to provide efficient cleaning performance. The anti-redeposition performance of high efficiency detergent formulations may also last longer in small water environments. In addition, to facilitate efficiency, formulations are envisioned that allow the wash water to be more easily washed away from the garment or centrifugally dehydrated from the garment in a washer.

  As water usage is reduced in high efficiency machines, liquid softener formulations and "soft-agent" (additional softener / detergent functions) single addition formulations may also be required to change . The washer-added softener is placed in the rinsing cycle of these machines. Medium chain head group surfactants or alkylene cross-linked surfactants can be used in formulations that provide softness in addition to cleaning.

  Medium chain head group surfactants or alkylene bridges disclosed herein to provide high concentration formulations, or “environmentally friendly” formulations, or formulations that perform well in high efficiency washers Laundry detergents and additives containing surfactants are envisioned. Detergents or additives are envisioned that have at least some degree of at least one of the above-mentioned advantages or desirable properties, or combinations of two or more of these advantages. Inclusions envisioned for use in such laundry detergents and additives are found in the following paragraphs.

  In addition to surfactants as described above, laundry detergent compositions generally contain other ingredients for various purposes. Some of the inclusions are also described below.

(Builder and alkaline agent)
Builders and alkaline agents are envisioned for use in the formulations of the present invention.

  Any known builder system is suitable for use herein. The builder system includes aluminosilicate materials, silicates, polycarboxylates, and materials such as fatty acids, ethylenediaminetetraacetate, aminopolyphosphites, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Such sequestering agents are included.

  Polycarboxylates suitable for use herein include citric acid (preferably in the form of a water-soluble salt) and derivatives of succinic acid represented by the following formula:

ここで、Ｒは、Ｃ_{１０−２０}アルキル又はアルケニル、好ましくは、Ｃ_１２〜Ｃ_１６であり、あるいは、Ｒは、ヒドロキシ置換基、スルホ置換基、スルホキシ置換基、又はスルホン置換基で置換され得る。特定の例には、ラウリルコハク酸塩、ミリスチルコハク酸塩、パルミチルコハク酸塩、２−ドデセニルコハク酸塩、又は２−テトラデシルコハク酸塩が含まれる。コハク酸塩ビルダーは、好ましくは、ナトリウム塩、カリウム塩、アンモニウム塩、及びアルカノールアンモニウム塩を含む水溶性塩の形態で使用される。

Where R is C _10-20 alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or R can be substituted with a hydroxy substituent, a sulfo substituent, a sulfoxy substituent, or a sulfone substituent . Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, or 2-tetradecyl succinate. Succinate builders are preferably used in the form of water soluble salts including sodium, potassium, ammonium and alkanol ammonium salts.

  Other suitable polycarboxylates are oxodisuccinate and a mixture of monosuccinate and disuccinate tartrate as disclosed in US Pat. No. 4,663,071.

In particular, in the case of liquid detergent compositions, the fatty acid builders suitable for use herein are C ₁₀ -C ₁₈ fatty acids and soaps corresponding thereto, of the or unsaturated saturated. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Preferred builder systems for liquid compositions are based on dodecenyl succinic acid and citric acid.

Some examples of alkaline agents, alkali metals (Na, K, or NH ₄₎ contained hydroxides, Tansanshio, citrate, and bicarbonate.

  In the case of powder detergent compositions, the builder or alkalinizing agent is typically comprised between 1% and 95% of the composition. In the case of liquid compositions, the builder or alkalinizing agent typically comprises 1% to 60%, alternatively 1% to 30%, alternatively 2% to 15%. See U.S. Pat. No. 5,929,022. This teaching is incorporated herein by reference, and much of the discussion above arises from that patent. Other builders are disclosed in WO 99/05242. This content is incorporated herein by reference.

(Additional enzyme)
In addition to the lipase, the detergent composition may contain one or more enzymes. The enzyme provides cleaning performance and / or garment care benefits. Enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase Or mixtures thereof.

  Preferred combinations are lipases and other known applicable enzymes such as proteases, amylases, cutinases and / or cellulases used in combination with the lipolytic enzyme variant D96DL in an amount of 50 LU-8500 LU per liter of wash solution It is a detergent composition containing the liquid mixture of.

  Suitable cellulases include both bacterial cellulases and fungal cellulases. Preferably, it will have an optimum pH of 5 to 9.5. Suitable cellulases are disclosed in US Pat. No. 4,435,307. The patent discloses a cellulase derived from a fungus obtained from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275, and DE-A-2224732.

  An example of such a cellulase is the cellulase produced by the strain Humicola insolens (Humicola grisea var. Thermoidea), in particular by the strain Humicola DSM1800. Another suitable cellulase is a cellulase from Humicola insolens, having a molecular weight of about 50,000, an isoelectric point of 5.5, and having 415 amino acid units. Particularly preferred cellulases are cellulases that have the benefit of color care. Examples of such cellulases are disclosed in EP-A-91202879.2.

  Peroxidase enzymes are used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", i.e. to prevent the dyes or pigments removed during the washing operation from moving from the substrate to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in WO 89/099813 and EP-A-91202882.6.

  Cellulase and / or peroxidase is usually included in the detergent composition in an amount of 0.001% to 2% by weight of the active enzyme relative to the detergent composition.

  Preferred commercially available protease enzymes are sold by Novozymes under the trade names Alcalase®, Savinase®, Primease®, Durazym®, and Esperase®. Those sold under the trade names Maxatase (R), Maxcal (R), and Maxapem (R) by DSM, DuPont Industrial Biosciences (formerly And those sold under the trade names Optilean (R) and Optimase (R) by Danisco. Other proteases are disclosed in US Pat. No. 5,679,630, which can be included in a detergent composition. The protease enzyme may be included in the detergent composition in an amount of active enzyme from about 0.0001% to about 2% by weight relative to the composition.

  A preferred protease referred to herein as “protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature. The carbonyl hydrolase variant is located at a position in the carbonyl hydrolase equal to the +76 position according to the numbering of Bacillus amyloliquefaciens subtilisin as disclosed in US Pat. No. 5,679,630. By substituting amino acid residues with different amino acids, preferably also +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, One or more amino acids equal to those selected from the group consisting of +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 Derived from the precursor carbonyl hydrolase by replacing the amino acid residue in combination with the residue position with a different amino acid. The teachings of the above US patents are incorporated herein by reference.

  Also suitable are cutinases (EC 3.1.1.50) which can be considered as a specific type of lipase, ie a lipase that does not require surface activation. Addition of cutinase to a detergent composition is disclosed, for example, in WO 88/09367.

  Cutinase is usually included in the detergent composition in an amount of 0.0001% to 2% by weight of the active enzyme relative to the detergent composition.

  Amylase (α and / or β) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl® amylase, Fungamyl® amylase, and BAN® amylase (Novozyme).

  The enzyme may be of any suitable origin such as vegetable origin, animal origin, microorganism origin, fungus origin, and / or yeast origin. See U.S. Pat. No. 5,929,022. The teachings of that patent are incorporated herein by reference. Much of the above discussion stems from the patent. Preferred compositions optionally contain a combination of multiple enzymes or a single enzyme. The amount of each enzyme is generally in the range of 0.0001% to 2%.

  Other enzymes and materials used with the enzymes are disclosed in WO 99/05242. The contents of this publication are incorporated herein by reference.

(Auxiliary agent)
The detergent composition optionally includes one or more soil suspending agents or recontamination inhibitors in an amount from about 0.01 wt% to about 5 wt%, alternatively less than about 2 wt%. Recontamination inhibitors include anti-redeposition agents, soil release agents, or combinations thereof. Suitable agents are disclosed in U.S. Pat. No. 5,929,022, and include water soluble ethoxylated amines having soil removal and anti-redeposition properties. Examples of such soil release agents and anti-redeposition agents include ethoxylated tetraethylenepentamine. Further suitable ethoxylated amines are disclosed in US Pat. No. 4,597,898. The teachings of that patent are incorporated herein by reference. Another group of preferred soil removal agents / anti-redeposition agents are the cationic compounds disclosed in EP-A-111965. Other soil removal / anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in EP 111984, EP 1 12592. Zwitterionic polymers, and the amine oxides disclosed in US Pat. No. 4,548,744. These teachings are incorporated herein by reference.

  Other soil removal agents and / or anti-redeposition agents known in the art can also be used in the composition. Another type of preferred anti-redeposition agent includes carboxymethylcellulose (CMC) materials.

  Anti-redeposition polymers can be included in the HDL formulations disclosed herein. It is preferred to maintain the amount of anti-redeposition polymer below about 2%. For amounts above about 2%, the anti-redeposition polymer can cause the formulation to become unstable and / or thicker than necessary.

  An amount of about 0.1% to about 5% of a soil release agent is also envisioned as an optional ingredient (see, eg, US Pat. No. 5,929,022).

  An amount of about 0.1% to about 10%, more preferably about 0.5% to about 5%, more preferably about 0.8% to about 3% of a chelating agent is also envisioned as an optional ingredient. (See, for example, US Pat. No. 5,929,022).

  A 0% to about 6% amount of polymeric dispersant is also envisioned as an optional component of the detergent compositions disclosed herein (see, eg, US Pat. No. 5,929,022).

  An amount of soap suds suppressant of from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, and even more preferably from about 1% to about 7% is also optional for the detergent composition. As an ingredient (see, for example, US Pat. No. 5,929,022).

  Other ingredients that may be included in the liquid laundry detergent include fragrances that optionally include ingredients such as aldehydes, ketones, esters, and alcohols. Additional compositions that can be included are carriers, hydrotropes, processing aids, dyes, pigments, solvents, bleaches, bleach activators, fluorescent whitening agents, and enzyme-stabilized packaging systems.

Co-surfactants and fatty acids disclosed in US Pat. No. 4,456,1998, the teachings of which are incorporated herein by reference, can be included in the detergent composition. By using in combination with anionic surfactants, these improve laundry performance. These examples, chlorides, borides and methylsulfate _C 8 _{-C 16} alkyltrimethylammonium _salts, C 8 _{-C 16} alkyl di (hydroxyethyl) methylammonium _salts, C 8 _{-C 16} alkyl hydroxyethyl dimethyl ammonium salts, and include _C 8 _{-C 16} alkyl trimethylammonium salt.

  Similar to what is taught in U.S. Pat. No. 4,456,1998, the compositions herein are also from about 0.25% to about 12%, preferably from about 0.5% to about 8%. % By weight, more preferably from about 1% to about 4% by weight of co-surfactant. The co-surfactant is a specific quaternary ammonium surfactant, quaternary diammonium surfactant, amine surfactant, diamine surfactant, amine oxide surfactant, and di (amine oxide) surfactant. Selected from the group consisting of Quaternary ammonium surfactants are particularly preferred.

  The quaternary ammonium surfactant can have the following chemical formula:

ここで、Ｒ^２は、アルキル鎖中に約８〜約１８の炭素原子を有するアルキル基又はアルキルベンジル基であり、各Ｒ^３は、−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ_２ＣＨ（ＣＨ_２ＯＨ）−、−ＣＨ_２ＣＨ_２ＣＨ_２−及びこれらの混合物からなる群から選ばれ、各Ｒ^４は、Ｃ_１〜Ｃ_４アルキル、Ｃ_１〜Ｃ_４ヒドロキシアルキル、ベンジル、２つのＲ^４基が合わさって形成される環構造、−ＣＨ_２ＣＨＯＨＣＨＯＨＣＯＲ^６ＣＨＯＨＣＨ_２ＯＨからなる群から選ばれる。ここで、Ｒ^６は、約１０００未満の分子量を有し、ｙが０でない場合、水素を有する任意のヘキソース又はヘキソースポリマーである。Ｒ^５は、Ｒ^４と同じであるか、Ｒ^２及びＲ^５の炭素原子の総数が最大で約１８であるアルキル鎖である。それぞれのｙは０〜約１０であり、ｙの値を足し合わせたものは、０〜約１５である。Ｘは、任意の相溶性アニオンである。

Here, R ² is an alkyl group or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain, and each R ³ is —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ). —, —CH ₂ CH (CH ₂ OH) —, —CH ₂ CH ₂ CH ₂ — and a mixture thereof, wherein each R ⁴ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxy It is selected from the group consisting of alkyl, benzyl, a ring structure formed by combining two R ⁴ groups, and —CH ₂ CHOHCHOHCOR ⁶ CHOHCH ₂ OH. Where R ⁶ is any hexose or hexose polymer having a molecular weight of less than about 1000 and having hydrogen when y is not zero. R ⁵ is the same as R ⁴ or an alkyl chain in which the total number of carbon atoms in R ² and R ⁵ is at most about 18. Each y is 0 to about 10, and the sum of the values of y is 0 to about 15. X is any compatible anion.

Of the above, alkyl quaternary ammonium surfactants are preferred, and in particular, when R ⁵ is selected from the same group as R ⁴ , mono long chain alkyl surfactants described in the above formula are preferred. Optimum quaternary ammonium _surfactants, C 8 _{-C 16} alkyl trimethylammonium chloride, bromide, and _{methylsulfate,} C 8 _{-C 16} alkyl di (hydroxyethyl) methyl ammonium chloride, bromide, and methyl sulfate, C ₈ -C ₁₆ alkyl hydroxyethyl diethyl ammonium chloride, bromide, and methylsulfate, and C ₈ -C ₁₆ alkyl trimethylammonium chloride, bromide, and methylsulfate. Of the above, decyltrimethylammonium sulfate, lauryltrimethylammonium chloride, myristyltrimethylammonium bromide, and coconut trimethylammonium chloride and coconut trimethylammonium sulfate are particularly preferred.

U.S. Patent No. 4561998, in the cold water wash conditions, of less than about _{65 ° F (18.3 ℃),} C 8 ~C 10 alkyl trimethyl ammonium surfactants, the longer the alkyl chain of the specification It also provides that it is particularly preferred because it has a lower Kraft boundary than quaternary ammonium surfactants, thereby lowering the crystallization temperature.

  The quaternary diammonium surfactant may be of the following formula:

ここで、Ｒ^２置換基、Ｒ^３置換基、Ｒ^４置換基、Ｒ^５置換基、ｙ、及びＸ置換基は、第四級アンモニウムについて先に定義した通りである。これらの置換基はまた、好ましい第四級アンモニウム界面活性剤に対応する第四級ジアンモニウム界面活性剤を提供するように選ばれると好ましい。Ｃ_８〜Ｃ_１６アルキルペンタメチルエチレンジアンモニウムクロリド、ブロミド、及びＣ_８〜Ｃ_１６アルキルペンタメチルエチレンジアンモニウムスルフェートが特に好ましい。

Here, the R ² substituent, R ³ substituent, R ⁴ substituent, R ⁵ substituent, y, and X substituent are as defined above for quaternary ammonium. These substituents are also preferably chosen to provide a quaternary diammonium surfactant corresponding to the preferred quaternary ammonium surfactant. C ₈ -C ₁₆ alkyl pentamethyl ethylene chloride, bromide, and _C 8 _{-C 16} alkyl pentamethyl ethylene diammonium sulfate is particularly preferred.

  The amine surfactants useful herein are as follows:

ここで、Ｒ^２置換基、Ｒ^３置換基、Ｒ^４置換基、Ｒ^５置換基、及びｙ（ｙは係数であり、置換基ではない）は、第四級アンモニウム界面活性剤について先に定義された通りである。Ｃ_{１２−１６}アルキルジメチルアミンが特に好ましい。

Where R ² substituent, R ³ substituent, R ⁴ substituent, R ⁵ substituent, and y (y is a coefficient, not a substituent) are defined above for the quaternary ammonium surfactant. It has been done. C _12-16 alkyldimethylamine is particularly preferred.

  The diamine surfactant in this specification is as follows.

ここで、Ｒ^２置換基、Ｒ^３置換基、Ｒ^４置換基、Ｒ^５置換基、及びｙは、先に定義された通りである。Ｃ_１２〜Ｃ_１６アルキルトリメチルエチレンジアミンが好ましい。

Here, the R ² substituent, the R ³ substituent, the R ⁴ substituent, the R ⁵ substituent, and y are as defined above. C ₁₂ -C ₁₆ alkyltrimethylethylenediamine is preferred.

  The amine oxide surfactants useful herein are as follows:

ここで、Ｒ^２置換基、Ｒ^３置換基、Ｒ^４置換基、Ｒ^５置換基、及びｙは、第四級アンモニウム界面活性剤について先に定義された通りである。Ｃ_{１２−１６}アルキルジメチルアミンオキシドが特に好ましい。

Here, the R ² substituent, R ³ substituent, R ⁴ substituent, R ⁵ substituent, and y are as defined above for the quaternary ammonium surfactant. C _12-16 alkyldimethylamine oxide is particularly preferred.

  The di (amine oxide) surfactant in the present specification is represented by the following formula.

ここで、Ｒ^２置換基、Ｒ^３置換基、Ｒ^４置換基、Ｒ^５置換基、及びｙは先に定義された通りである。Ｃ_{１２−１６}アルキルトリメチルエチレンジ（アミンオキシド）が好ましい。

Here, the R ² substituent, the R ³ substituent, the R ⁴ substituent, the R ⁵ substituent, and y are as defined above. C _12-16 alkyltrimethylethylenedi (amine oxide) is preferred.

  Other common cleaning additives are disclosed in US Pat. No. 7,326,675 and WO 99/05242. Such cleaning additives include bleaching agents, bleach activators, foaming promoters, other dispersant polymers (eg, available from BSF Corporation or Dow Chemical), colored speckles, silver care, discoloration Inhibitors and / or anticorrosives, dyes, pigments, fillers, bactericides, hydrotropes, antioxidants, enzyme stabilizers, scent promoters (pro-perfume), carriers, processing aids, solvents, pigment migration inhibition Clarified to include agents, brighteners, structural elasticizers, softeners, antiwear agents, and other garment care agents, surface and skin care agents. Suitable examples and use amounts of such other cleaning additives can be found in US Pat. Nos. 5,576,282, 6,306,812, 6,326,348, and WO 99/05242. These teachings are incorporated herein by reference.

(fatty acid)
Similar to that disclosed in US Pat. No. 4,456,1998, the detergent composition may comprise fatty acids containing from about 10 to about 22 carbon atoms. The fatty acid may also contain about 1 to about 10 ethylene oxide units in the hydrocarbon chain. Suitable fatty acids are saturated or unsaturated, and are plant or animal esters (eg, palm kernel oil, palm oil, coconut oil, babasque oil, safflower oil, tall oil, castor oil, tallow, and fish oils, fats and these In combination) or synthetically prepared (eg, through the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fischer-Tropsch process). Saturated fatty acids suitable for use in detergent compositions include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Suitable unsaturated fatty acid species include palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. Examples of preferred fatty acids are saturated _C 10 _{-C 14} (coconut) fatty acids, by weight of lauric acid and myristic acid ratio of about 5: 1 to about 1: 1 (preferably about 3: 1) mixture of, and the lauric acid / Mixed with a mystinic acid mixture and oleic acid in a weight ratio of about 4: 1 to about 1: 4 (lauric acid / mistynic acid: oleic acid).

  U.S. Pat. No. 4,507,219 discloses sulfonate surfactants as being suitable for use with the co-surfactants identified above. The disclosures in US Pat. Nos. 4,456,1998 and 4,507,219 relating to cosurfactants are incorporated herein by reference.

(Soft Taggent)
For example, softgent techniques such as those disclosed in US Pat. Nos. 6,949,498, 5,466,394, and 5,622,925 can be used in detergent compositions. “Softgent” means a detergent that exhibits a softening function that can be applied at the start of the wash cycle to simultaneously wash and soften the fabric. A stable and aqueous powerful liquid laundry detergent composition comprising a fabric softener that provides extraordinary cleansing and provides fabric softening and anti-static benefits with medium chain head group surfactants or alkylene cross-linked surfactants Things are made.

  Some suitable soft detergent compositions comprise from about 0.5% to about 10%, preferably from about 2% to about 7%, by weight of a quaternary ammonium fabric softener of the formula More preferably, it contains about 3 wt% to about 5 wt%.

ここで、Ｒ_１及びＲ_２は、Ｃ_１〜Ｃ_４アルキル、Ｃ_１〜Ｃ_４ヒドロキシアルキル、ベンジル、及び−（Ｃ_２Ｈ_４Ｏ）_ｘ（ここで、ｘは、２〜５の値である）からなる群から独立して選ばれ、Ｘはアニオンであり、（１）Ｒ_３及びＲ_４は、それぞれＣ_８〜Ｃ_１４アルキルであるか、又は（２）Ｒ_３は、Ｃ_８〜Ｃ_２２アルキルであり、Ｒ_４は、Ｃ_１〜Ｃ_１０アルキル、Ｃ〜Ｃ_１０ヒドロキシアルキル、ベンジル、及び−（Ｃ_２Ｈ_４Ｏ）_ｘＨ（ここで、ｘは２〜５の値である）からなる群から選ばれる。

Here, R ₁ and R ₂ are C _{1 to} C ₄ alkyl, C _{1 to} C ₄ hydroxyalkyl, benzyl, and — (C ₂ H ₄ O) _x (where x is a value of 2 to 5). selected from the group consisting of certain) independently, X is an anion, (1) _{R 3} and _{R 4} are the _C 8 _{-C 14} alkyl, respectively, or (2) _{R 3 is C} 8 ~ C ₂₂ alkyl, R ₄ is C _{1 to} C ₁₀ alkyl, C to C ₁₀ hydroxyalkyl, benzyl, and — (C ₂ H ₄ O) _x H (where x is a value from 2 to 5). ).

Preferred fabric softeners are mono long chain alkyl quaternary ammonium surfactants. Here, in the above formula, R ₁ , R ₂ , and R ₃ are each methyl, and R ₄ is C ₈ -C ₁₈ alkyl. Optimum quaternary ammonium surfactants, C ₈ -C ₁₆ alkyl trimethylammonium chloride, bromide, and methylsulfate. Among the above, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, coconut trimethyl ammonium chloride and methyl sulfate are particularly preferable.

Another preferred type of quaternary ammonium surfactants are the di-C ₈ -C ₁₄ alkyl dimethyl ammonium chloride or methyl sulfate, particularly preferably a di C ₁₂ -C ₁₄ alkyl dimethyl ammonium chloride. This type of material is particularly suitable for providing antistatic benefits to fabrics.

  Preferred soft agents include detergent compositions. In the detergent composition, the weight ratio of the anionic surfactant component to the quaternary ammonium softener is about 3: 1 to about 40: 1, more preferably about 5: 1 to 20: 1. It is.

(Odor control)
For example, odor control techniques such as those disclosed in US Pat. No. 6,878,695 can be used in detergent compositions.

  For example, a composition comprising one or more medium chain head group surfactants or alkylene cross-linked surfactants can further comprise a low degree of substitution cyclodextrin derivative and a fragrance. The cyclodextrin is preferably a functionally useful cyclodextrin. The composition can further comprise any material that is compatible with cyclodextrin and any material that is not compatible, and other optional ingredients. Such compositions can be used in various situations, preferably to trap unwanted molecules to control malodors. Malodor control includes malodorous molecules on inanimate surfaces such as carpeted fabrics, and on hard surfaces such as cooktops, dishes, floors, trash cans, ceilings, walls, carpet pads, air filters, and the like. It includes controlling malodorous molecules and malodorous molecules on biological surfaces such as skin and hair.

  The low substitution degree cyclodextrin derivatives useful herein are preferably selected from low substituted hydroxyalkyl cyclodextrins, low substituted alkylated cyclodextrins, and mixtures thereof. The low degree of substitution hydroxyalkyl β-cyclodextrin has an average degree of substitution of less than about 5.0, more preferably less than about 4.5, and even more preferably less than about 4.0. Preferred low substituted alkylated cyclodextrins have an average degree of substitution of less than about 6.0, more preferably less than about 5.5, and even more preferably less than about 5.0.

  The detergent composition can include a mixture of cyclodextrin and its derivatives, such that the mixture has an average degree of substitution that is substantially equal to the previously disclosed low-substituted cyclodextrin derivatives. Such cyclodextrin mixtures are higher than the less substituted cyclodextrin derivatives disclosed herein, such that the cyclodextrin mixture has an average degree of substitution that is virtually equal to that of the low degree of cyclodextrin. It is preferred to include highly substituted cyclodextrin derivatives (with an average degree of substitution) and non-derivatized cyclodextrins. For example, a composition comprising a cyclodextrin mixture comprising about 0.1% underivatized β-cyclodextrin and about 0.4% hydroxypropyl β-cyclodextrin with an average degree of substitution of about 5.5 Shows similar ability to capture undesired molecules as similar compositions comprising low substituted hydroxypropyl β-cyclodextrin with an average degree of substitution of about 3.3. Such cyclodextrin mixtures typically can adsorb odors more broadly by complexing with a wide range of unwanted molecules having a wide range of molecular sizes, especially malodorous molecules. Preferably, at least part of the cyclodextrin mixture is α-cyclodextrin and derivatives thereof, γ-cyclodextrin and derivatives thereof, and / or β-cyclodextrin and derivatives thereof, more preferably α-cyclodextrin or derivatives thereof. an α-cyclodextrin derivative and a mixture of derivatized β-cyclodextrin, more preferably a mixture of derivatized α-dextrin and derivatized β-dextrin, optimally hydroxypropyl A mixture of α-cyclodextrin and hydroxypropyl β-cyclodextrin and / or a mixture of methylated α-cyclodextrin and methylated β-cyclodextrin.

  Functionality in detergent compositions because cyclodextrins can adsorb (ie, complex) various undesirable molecules such as malodorous molecules in solution when the composition is applied to a surface containing unwanted molecules. The voids within the cyclodextrin that are available for use must be substantially unfilled (ie, the cyclodextrin is not complexed and free) or is weak It needs to be filled only with the complexing material. Underivatized (normal) β-cyclodextrin may be present at room temperature in an amount up to a solubility limit of about 1.85% (about 1.85 g in 100 grams of water). Β-cyclodextrin is not preferred in compositions that require higher amounts of cyclodextrin than the water solubility limit. Underivatized β-cyclodextrin is generally not preferred when the composition includes a surfactant. This is because underivatized β-cyclodextrin adversely affects the surface activity of most preferred surfactants that are compatible with derivatized cyclodextrin.

  The low substituted cyclodextrin derivative functionally available in the odor control composition is typically at least about 0.001%, preferably at least about 0.01% by weight of the detergent composition. More preferably, it is at least about 0.1% by weight. The total amount of cyclodextrin in the composition is at least equal to or greater than the amount of functionally available cyclodextrin. The amount of functionally available is typically at least about 10 wt%, preferably at least about 20 wt%, more preferably at least about 30 wt%, relative to the total amount of cyclodextrin in the composition. It is.

  A concentrated composition may be used. When a concentrated product is used, i.e., the total amount of cyclodextrin used is about 3% to about 60%, preferably about 5% to about 40%, by weight of the concentrated composition. In this case, it is preferred to dilute the concentrated composition before treating the fabric to avoid staining. Preferably, the concentrated cyclodextrin composition is about 50% to about 6000%, more preferably about 75% to about 2000%, optimally about 100% by weight of the concentrated composition. Dilute with ~ 1000 wt% water. The resulting diluted composition has a total cyclodextrin usage concentration as described above and a functionally available cyclodextrin usage concentration. For example, the total cyclodextrin use concentration is from about 0.1% to about 5% by weight relative to the diluted composition, and the functionally available cyclodextrin use concentration is at least about the dilute composition. 0.001% by weight.

(Form)
The detergent composition can take any number of forms and any type of delivery system, such as ready-to-use, dilutable, wipes, or the like.

  For example, the detergent composition can be a dilutable fabric detergent. The dilutable fabric detergent is an isotropic liquid, a surfactant structured liquid, a granular powder, a spray-dried powder, or a dry mixed powder, a form, a paste, a molded solid, a water-soluble sheet, or known to those skilled in the art Any other laundry detergent form may be used. A “dilutable” fabric detergent composition may be diluted with water or a non-aqueous solvent in a ratio of greater than 100: 1 to create a liquid that suitably treats the fabric for purposes of this disclosure. Defined as a product intended to be used. “Environmentally friendly” compositions (such as Fantastic®, Windex®, and the like in today's market) are added to the bottle for final reconstitution It can be formulated to be a concentrate.

  The detergent composition can also be formulated as a pod such as a gel or gel packet, or a dishwasher on the market today. Water-soluble sheets, sachets, or pods are disclosed in US 2002/0187909. These teachings are hereby incorporated by reference and are assumed to be in a preferred form. The detergent composition can also be deposited on a wiper or other substrate.

(Polymer foaming accelerator)
In some embodiments, polymeric foam promoters such as those disclosed in US Pat. No. 6,903,064 may be used in detergent compositions. For example, the composition includes an effective amount of a polymer foam volume and a foam persistence promoter. These polymeric materials provide increased foam volume during cleaning and sustained foaming.

Examples of polymeric foam stabilizers suitable for use in the composition are:
(I) a polymer having at least one monomer unit represented by the following formula;

ここで、Ｒ^１、Ｒ^２及びＲ^３のそれぞれは、水素、Ｃ_１〜Ｃ_６アルキル、及びこれらの混合物からなる群から独立して選ばれ、ＬはＯであり、ＺはＣＨ_２であり、ｚは約２〜約１２から選ばれる整数であり、Ａは、ＮＲ^４Ｒ^５（ここで、Ｒ^４及びＲ^５のそれぞれは、水素、Ｃ_１〜Ｃ_８アルキル、及びこれらの混合物から独立して選ばれる）であり、ＮＲ^４Ｒ^５は、４〜７の炭素原子を含み、必要に応じて追加のヘテロ原子を含み、必要に応じてベンゼン環に縮合されており、且つ必要に応じてＣ_１〜Ｃ_８ヒドロカルビルで置換されている複素環を形成する。

Here, each of R ¹ , R ² and R ³ is independently selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, and mixtures thereof, L is O, and Z is CH ₂ , Z is an integer selected from about 2 to about 12, and A is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are each independently hydrogen, C ₁ -C ₈ alkyl, and mixtures thereof) NR ⁴ R ⁵ contains 4-7 carbon atoms, optionally contains additional heteroatoms, optionally condensed to a benzene ring, and optionally To form a heterocyclic ring substituted with C ₁ -C ₈ hydrocarbyl.

(Ii) a proteinaceous foam stabilizer having an isoelectric point of about 7 to about 11.5;
(Iii) zwitterionic polymer foam stabilizer: or
(Iv) A mixture of these.
Preferably, the exemplary polymeric foam stabilizers described above have a molecular weight of about 1000 to about 2 million, more preferably the molecular weight is about 5000 to about 1000000.

(How to wash the fabric)
A fabric washing method using a medium chain head group surfactant or an alkylene cross-linking surfactant is envisaged. The method places the fabric item to be washed in a high efficiency washer or a normal (non-efficiency) washer, and when the machine is operating in a wash cycle, the detergent composition concentration in water is about It involves placing a sufficient amount of the detergent composition to be from 0.001% to about 5% by weight. A high-efficiency machine is defined by the Soap and Detergent Association as any machine that uses 20% to 66% water and uses only 20% to 50% energy compared to a conventional regular stirred washer. (See SDA “Washers and Detergent” publication 2005; www.cleaning101.com). A wash cycle is activated or initiated to wash the fabric article. Hand washing using the detergent composition of the present invention is also envisioned. In particular, the detergent is advantageous for hand washing and cold water washing of fine and delicate fabrics.

  Accordingly, in one aspect, the present invention provides that the one or more fabric articles are at a temperature below 30 ° C, preferably at a temperature between 5 ° C and 30 ° C, in the presence of the detergent of the present invention as described herein. A method comprising washing in water.

(Other uses)
Medium chain head group surfactants or alkylene cross-linked surfactants have considerable value for laundry detergents, but other end uses also need to benefit from their use. Accordingly, surfactants should also have value in applications where greasy substrates require removal and cleaning. Such applications include, for example, household detergents, oil-based detergents, disinfectants and disinfectants, light liquid detergents, household hard and soft surface detergents, automatic dishwashing detergents, rinsing aids, laundry additives, carpets Detergents, stain treatment agents, soft detergents, industrial and commercial detergents, oil-based cleaners, oven cleaners, vehicle cleaners, transport cleaners, drain pipe cleaners, industrial detergents, foaming agents, antifoaming agents, business Detergents, cleaning detergents, glass detergents, graffiti removers, detergency removers, concrete cleaners, metal / mechanical parts detergents, and food industry detergents, and removal of greasy soils are particularly advantageous at or below room temperature Other similar applications that are realized are included. Detergents may be beneficial for certain personal care applications such as hand soaps and liquid detergents, shampoos, and other hair / scalp cleaning products, especially oily / greasy hair, scalp, and skin . They are also beneficial when effective with hot or cold water.

  The following examples are merely illustrative of the invention and those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

(Preparation of sodium 2-hexyl-1decyl sulfate)
2-Hexyl-1-decanol (100.3 g) was added to a 1 L flask equipped with a mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (500 mL) was added and the mixture was stirred. Sulfamic acid (42.7 g) and urea (10.2 g) were added. The mixture was slowly heated to reflux (at 105 ° C.) and continued to reflux for 7 hours. The mixture was cooled. Urea and remaining sulfamic acid were removed by filtration. The mixture was concentrated to remove 1,4-dioxane. Methanol was added to 2-hexyl-1-decyl sulfate ammonium salt, and then 50% aqueous NaOH was added to bring the pH to about 10.4. Methanol was removed. ¹ HNMR analysis showed significant impurities. The product was purified using a separatory funnel and 50:50 ethanol: deionized water and petroleum ether as the extractant. The resulting mixture contained sodium 2-hexyl-1-decyl sulfate. The mixture was stripped and analyzed (96.9% activity according to ¹ HNMR).

(Preparation of 9-octadecanol)
A 1 L flask containing shavings magnesium (13.3 g) was flame dried. A reflux condenser and an additional funnel were attached so that each was fitted with a drying tube. A mechanical stirrer was also used to flame dry all glassware. Anhydrous tetrahydrofuran (THF, 100 mL) was added to the shaved magnesium. An additional funnel was charged with 1-bromononane (100.0 g) and dry THF (50 mL). The 1-bromononane solution was slowly added to the magnesium and the reaction started immediately. 1-Bromononane was added at a rate that maintained the THF at reflux. After completing the alkali halide addition, the reaction mixture was stirred for an additional 30 minutes. Another additional funnel was charged with nonanol (68.7 g) and dry THF (50 mL). While maintaining the temperature at about 60 ° C., the nonanol solution was added as quickly as possible. After completing the aldehyde addition, the reaction mixture was stirred at 60 ° C. for an additional 30 minutes. After cooling, an equivalent amount of hydrochloric acid (25% by weight aqueous HCl) was added. After adding deionized water (50 mL), the THF layer was separated and concentrated. 9-Octadecanol was purified using a column equipped with neutral rockman I alumina and 1: 1 hexane: diethyl ether as eluent. 1H NMR analysis showed 9-octadecanol with a purity of about 92%.

(Preparation of sodium 9-octadecyl sulfate)
9-Octadecanol (64.9 g, 0.24 mol) was added to a 1 L flask equipped with a mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (300 mL) was added and the mixture was stirred. Sulfamic acid (24.4 g, 0.25 mol) and urea (5.0 g) were added. The mixture was slowly heated to reflux (at 105 ° C.) and continued to reflux for 14 hours. ¹ HNMR indicated that the reaction was almost complete. The mixture was cooled. Urea and remaining sulfamic acid were removed by filtration. The mixture was concentrated to remove 1,4-dioxane. Methanol was added to 9-octadodecyl sulfate ammonium salt followed by 50% aqueous NaOH to bring the pH to about 10.6. Methanol was removed. ¹ H NMR analysis showed significant impurities. The product was purified using a column with Brockman I neutral alumina and 50:50 methanol: deionized water as the eluent. The resulting mixture contained 9-octadecyl sodium sulfate. The mixture was stripped and analyzed (82.1% solids at 105 ° C., 99.3% activity according to ¹ HNMR).

(Test procedure for laundry detergent samples)
After putting the laundry detergent into the washer (to give 0.1% activity in the wash solution), a soiled / stained fabric swatch was attached to the pillowcase. The washing temperature was 60 ° F. The rinsing temperature was 60 ° F. The sample was removed from the pillowcase, dried and ironed. Samples were scanned to determine L ^* a ^* b ^* values. This value was used to calculate the soil removal index (SRI) for various samples. Finally, ΔSRI was calculated. The ΔSRI is the same as the SRI of the experimental sample minus the SRI of the standard laundry detergent formulation (or control) determined in advance. If | ΔSRI | ≧ 0.5, the difference can be perceived with the naked eye. If the value of ΔSRI is greater than or equal to 0.5, the sample is excellent. If ΔSRI is less than or equal to −0.5, the sample is inferior. If ΔSRI is greater than −0.5 and less than 0.5, the sample is considered the same as the standard.

  The following standard soiled / stained fabric swatches were used. That is, the thing which bacon fat, butter, cooked head, and beef tallow adhered to the cotton cloth ground was used. At least three samples for each type were used for each wash. The sample was stapled to the pillowcase for cleaning. An additional pillowcase is included to achieve a 6 pound weight.

  The same procedure was used to wash all of the pillowcases / swatches, taking care to ensure that the wash temperature, wash time, addition method, etc. were kept constant during the cold water wash process. When the cycle was complete, the swatch was removed from the pillowcase, dried in the rack with low heat, and gently and briefly pressed using a drying iron.

Using a Hunter LabScan® spectrophotometer, L ^* a ^* b ^* values were measured, SRIs of all types of samples were calculated, and the soil removal index (SRI) was calculated according to the following equation.

Table 1 provides formulation details. Control formulation (without lipase) and formulation A (with lipase) are Biosoft (R) S-101 (a product of Stepan. To make the corresponding sodium salt, linear alkylbenzene sulfonic acid was used. Neutralized in-situ sufficiently with NaOH (50%) to pH 8.4 (“NaLAS”), Neodol® 25-7 (product of Shell Chemicals, aliphatic alcohol ethoxylate). And C ₁₂ -C ₁₄ alcohol ethoxylate (3 EO) sodium sulfate (“NaAES (3 EO”). “Control” and Formulations B and D are lipases and medium chain head group surfactants or All are comparative formulations since they do not contain both of the alkylene crosslinking surfactants.

  Formulation B includes NaLAS, NaAES, and Neodol® 25-7 surfactant, and also includes 2-hexyl-1-decyl sodium sulfate, an alkylene crosslinking surfactant. Formulation B does not contain lipase and is intended as a comparative example.

  Formulation C is obtained by adding lipase to formulation B, and shows a positive effect on detergency by combining an alkylene cross-linking surfactant and a lipase.

  Formulation D includes NaLAS, NaAES, and Neodol® 25-7 surfactant, and further includes 9-octadecyl sulfate, medium chain head group surfactant. Formulation D does not contain lipase and is intended as a comparative example.

  Formulation E is obtained by adding lipase to formulation D, and shows a positive effect on detergency due to the combination of a medium-chain head group surfactant and lipase.

  Table 2 summarizes the cold water cleaning performance results of cotton fabrics treated with bacon fat, butter, cooked heads, and beef tallow stains. All formulations were tested at an activity level of 0.1%. The cleaning cycle was 30 minutes in the front type high efficiency washer. Target performance (ΔSRI equivalent to 0.0 for control and ΔSRI equivalent to 1.5 for formulation A) used in cold water wash (60 ° F) and cold water rinse (60 ° F) Controlled cold water detergent performance.

  As shown in Table 2, lipase was combined with either a medium chain head group surfactant (eg, 9-octadecyl sodium sulfate) or an alkylene cross-linked surfactant (eg, 2-hexyl-1-decyl sodium sulfate). According to one, a significant improvement is given for cleaning fat stains such as bacon fat, beef tallow or cooked heads compared to the same formulation without lipase. In the presence of a medium chain head group surfactant or an alkylene cross-linked surfactant, the overall change in ΔSRI (ie, ΔΔSRI) with lipase (ie, Formulation C vs. Formulation B, or Formulation E formulation) Object D) is significant. That is, a synergistic effect is evident between the lipase and the medium chain head group surfactant or the alkylene surfactant. In contrast, those that simply contain lipase (as in Formulation A vs. Control) in a conventional formulation that simply contains NaLAS, NaAES, and fatty alcohol ethoxylate surfactants are generally used in the soil removal index. It provided only a slight improvement.

  The previous examples are merely meant to be illustrative. The following claims define the scope of the inventive subject matter.

Claims (13)

Washing a soiled fabric item in water at a temperature below 30 ° C. in the presence of a detergent to obtain a washed fabric item comprising:
The detergent is
(A1) and medium chain headgroup surfactant is a 9-octadecanol or 8 sulfate hexadecanol,
(B) including lipase,
Wherein at detergents are the same in that it includes a branched medium chain surfactant, as compared to the stain removal index is provided in a similar manner without the said lipase, for at least one greasy soil, the same washing temperature Provide an improvement in soil removal index of at least 2.0 units,
Method. The detergent further comprises an anionic surfactant selected from the group consisting of linear alkylbenzene sulfonates, aliphatic alcohol sulfates, aliphatic alcohol ether sulfates, and mixtures thereof.
The method of claim 1. The detergent further comprises water;
The method of claim 1. The medium chain head group surfactant is 9-octadecanol sulfate,
The method of claim 1. The detergent further comprises an aliphatic alcohol ethoxylate,
The method of claim 1. The detergent comprises 1 to 20 wt% of the chain head base surfactant,
The method of claim 1. The detergent comprises 0.0001-1 wt% of the lipase,
The method of claim 1. The detergent comprises 0.001 to 0.5 wt% of the lipase,
The method of claim 1. The detergent is used in the form of a liquid, powder, paste, granule, tablet, molded solid, water-soluble sheet, water-soluble sachet, or water-soluble pod.
The method of claim 1. The detergent, water, and 1-20 wt% of the chain head base surfactant, 5 to 15% by weight, linear alkyl benzene sulfonic acid, fatty alcohol sulfates, fatty alcohol ether sulfates and, An anionic surfactant selected from the group consisting of these mixtures, and 5-15 wt% aliphatic alcohol ethoxylate,
The method of claim 1. The temperature of the water ranges from 5 ° C to 25 ° C;
The method of claim 1. The washing step includes using the detergent as a pre-stain or pre-soak for machine or hand washing;
The method of claim 1. Wherein the step of washing the lipid reduction performance of laundry products or laundry formulation or comprises using the detergent as an additive component or promotion component for improving the lipid removal performance,
The method of claim 1.